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Simultaneous co-doping of RuO2 and IrO2 into anodic TiO2 nanotubes: A

binary catalyst for electrochemical water splitting

Article  in  International Journal of Hydrogen Energy · December 2016

DOI: 10.1016/j.ijhydene.2016.12.018

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Simultaneous co-doping of RuO2 and IrO2 into

anodic TiO2 nanotubes: A binary catalyst for
electrochemical water splitting

Hyeonseok Yoo, Kiseok Oh, Yu Ri Lee, Kyung Ho Row, Gibaek Lee*,

Jinsub Choi**
Department of Chemistry and Chemical Engineering, Center for Molecular Catalysts and Applications (BK21 Plus
Program), Inha University, Yonghyun Dong 253, 22212, Incheon, Republic of Korea

article info abstract

Article history: The simultaneous doping of RuO2 and IrO2 catalysts into anodic TiO2 nanotubes (NTs) was
Received 7 October 2016 successfully achieved by single-step anodization. KRuO4 was used as the precursor for the
Received in revised form RuO2 dopant. However, for IrO2 doping, IrOx nanoparticles (NPs) were synthesized from
21 November 2016 IrCl3 as an intermediate species to avoid damage to the NTs by chloride ions during doping.
Accepted 7 December 2016 IrO4
generated from the IrOx NPs through selective dissolution in the electrolyte was
Available online 26 December 2016 simultaneously doped into the positively biased TiO2 NTs along with RuO2. The structural
features, NT length, and amount of catalyst doping were controlled by the concentration of
Keywords: HF in the electrolyte and the anodizing time. The binary-catalyst-doped TiO2 NTs exhibited
Anodization an outstanding onset potential of 0.84 V for the oxygen evolution reaction (OER). In addi-
TiO2 NTs tion, the amount of O2 gas evolved during the OER at 2.0 V was measured to be
RuO2 230 mmol cm
2 min
1 by gas chromatography, which corresponds to a faradaic efficiency of
IrO2 99%. The major oxidation states of the metals in the catalysts were found to be Ru4þ and
Water oxidation Ir4þ by X-ray photoelectron spectroscopy and transmission electron microscopy selected
area electron diffraction analysis, indicating the presence of RuO2 and IrO2 in the TiO2 NTs.
© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

electrochemical electrode for a long time [1‒6]. For example,

Introduction
Strength and resistance to corrosion are very important
criteria for electrochemical electrodes because they are often
exposed to harsh chemical conditions for long periods of time.
For example, the major anions in water purification and water
splitting, including Cl
and OH
, cause harsh conditions for
electrodes. Consequently, TiO2, which shows excellent phys-
ical and chemical stability, has been considered a favorable
dimensionally stable anodes (DSAs) that comprise TiO2 and
various catalysts on Ti electrodes are widely employed in in-
dustrial applications, and are still being investigated for other
electrochemical applications [6‒9]. Many methods for the
preparation of large-surface-area (and thus high-activity)
TiO2, such as the hydrothermal method [10,11], nanoparticle
preparation [12,13], and electrochemical anodization [14‒16],
have been reported. Perpendicularly grown, highly ordered
TiO2 nanotube (NT) materials with large surface areas are

* Corresponding author.
** Corresponding author.
E-mail addresses: gibaek@inha.ac.kr (G. Lee), jinsub@inha.ac.kr (J. Choi).
http://dx.doi.org/10.1016/j.ijhydene.2016.12.018
0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
6658 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 6 5 7 e6 6 6 4
typically prepared by anodization, and they do not require
additional binders to adhere to Ti substrates. However, since
TiO2 itself typically shows insulating properties, electro-
chemical catalysts must be introduced into the TiO2 by
coating or doping [17,18]. There are many reports on the
incorporation of noble metal or more economic catalysts into
TiO2 NTs to reduce their overpotential for water splitting ap-
plications [17‒24]. IrO2 and RuO2 are well-known catalysts for
various applications, including water oxidation [17‒19].
However, uniform doping of electrochemical catalysts into
TiO2 NTs is difficult due to their high-aspect-ratio structure.
Wu et al. [19] have reported that NiO can be loaded into anodic
TiO2 NT arrays by ultrasound-assisted deposition. Further-
more, Pozio et al. [20] have reported a method for introducing
Co3O4 into TiO2 NT arrays by electrodeposition in Co(NO3)2,
producing a material that was successfully used for water
oxidation. However, in most doping procedures, highly so-
phisticated and cumbersome pre- or post-processes are
necessary to evenly distribute the catalysts into the TiO2 NTs.
Recently, our group has developed two facile doping
methods that allow doping of RuO2 into TiO2 NTs, i.e., single-
step anodization [25], and potential shock [26,27]. In single-
step anodization, a negatively charged anion precursor, such
as RuO4
, can be doped during the formation of TiO2 NTs
through anodization. However, so far, only single foreign
components can be introduced by this process. Particularly in
the case of IrO2 doping, most possible precursors contain
chloride-based salts, which make uniform doping without
damage to the TiO2 NTs very difficult.
In this work, we have designed a novel process for doping
two components simultaneously into TiO2 NTs by single-step
anodization. In this process, KRuO4 is dissociated into RuO4
,
which is attracted to the positively biased TiO2 NTs. Further-
more, instead of using Ir-related salts directly, intermediate
IrOx nanoparticles (NPs), which generate IrO4
by the selective
dissolution of Ir2O3 in IrOx, are used as an IrO2 dopant pre-
cursor. We found that this facile single-step anodization
technique produces high-aspect-ratio TiO2 NTs containing the
binary catalyst, and that they exhibit outstanding water
oxidation performance.
Experimental
Electrochemical anodization and doping of RuO2 and IrO2
A Ti substrate with an area of 2.25 cm2 was washed in acetone
(15 min), ethanol (10 min), and deionized water (DI) (5 min) in
an ultra-sonicator. Chloride-based Ir precursors are difficult to
use as doping agents for TiO2 NTs because of the aggressive
properties of chloride ions [27]. Consequently, we first pre-
pared IrOx NPs, which can generate IrO4
in the electrolyte, as
an intermediate species. IrOx NPs were synthesized in aqueous
IrCl3 solution as previously reported by Zhao et al. [28]. In brief,
a 0.002 M IrCl3 solution (SigmaeAldrich) was titrated with 25 wt
% KOH solution to adjust the pH to 12. The mixture of IrCl3 and
KOH was then immediately heated at 90  C for 20 min, which
allowed the formation of 2e3 nm IrOx NPs dispersed in the
solution (Supporting Information Fig. S1). Then, 0.001 M
KRuO4, which was used as the ruthenium oxide precursor [25],
and the IrOx formed above were mixed directly into an elec-
trolyte consisting of 1 M H3PO4 þ 1 M NaOH þ 0.3
0.7 vol % HF
(48%, Sigma Aldrich), which is typically used in the formation
of anodic TiO2 NTs. Single-step anodization was then con-
ducted at 20 V by the potentiostatic method using a power
supply (Source Meter 2400, Keithley) for 1e8 h.
Characterizations
The morphological features of the materials were investigated
by high-resolution scanning electron microscopy (HR-SEM,
Hitachi S-4300SE, Hitachi). Simultaneously, energy dispersive
X-ray spectroscopy (EDS) was performed to confirm that the Ir
and Ru were successfully doped into the TiO2 NTs. X-ray
photoelectron spectroscopy (XPS, AlKa, VGESCALAB 220i-XL
spectrometer, Fisons) was performed to ascertain the phase of
each metal oxide at the bottom side of the anodic films. The
doping amount of Ru and Ir was measured by inductively
coupled plasma optical emission spectrometry (ICP-OES, Op-
tima 7300DV, Perkin Elmer) and field emission tunneling
electron microscopy (FE-TEM, JEM 2100F, JEOL).
Electrochemical performance tests
For electrochemical characterizations, linear sweep voltam-
metry (LSV) and electrochemical impedance spectroscopy
(EIS) were performed using a potentiostat (PGSTAT 302N,
Autolab) in 0.1 M KOH solutions. A three-electrode system
consisting of a Pt electrode and a Ag/AgCl 3 M KCl electrode as
the counter and reference electrodes, respectively, was used.
For LSV, the potential window of 0.0e2.2 V was investigated at
a scan rate of 20 mV s
1. The frequency for EIS was optimized
from 0.01 to 105 Hz with an amplitude of 0.1 V at an applied
potential of 1.26 V. The O2 gas evolved at 2.0 V for 1 min was
gathered in a gas-tight syringe and analyzed using a 6500GC
gas chromatography system (YL instrument) (Supporting
Information Fig. S2). Calibration using O2 and N2 gas with
purities of 99.99% was performed before quantitative analysis
of the O2 gas (Supporting Information Fig. S3). A column for
the separation of O2 gas (HP-MoleSeive 19091P MS8, 30 m
length, 0.32 mm diameter, 25 mm film thickness, Agilent) was
incorporated into the GC system to detect O2 from the gaseous
specimens. The column was activated in an oven maintained
at 280  C overnight before measurement, and the temperature
was fixed at 50  C during measurement. The gas as the mobile
phase and the gaseous samples were pumped through the
column at a rate of 1.7 mL min
1. A thermal conductivity de-
tector (TCD) was employed to sense the O2 gas at 200  C. All
measurements were conducted for 10 min to detect O2 suffi-
ciently. At each step, the column was regenerated to remove
the poisonous gases, such as water vapor and CO2, for more
precise analysis.
Results and discussion
The SEM images presented in Fig. 1 show that, unlike the
pristine TiO2 NTs (PNTs, Fig. 1aec), the IrO2eRuO2-doped TiO2
NTs (IRNTs, Fig. 1def) feature NT pores partially blocked by
IrOxeTiO2 particles (A in Fig. 1d). However, pores of ca. 100 nm
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 6 5 7 e6 6 6 4 6659

Fig. 1 e SEM images of PNTs (aec) and IRNTs (def), which were prepared in an electrolyte containing 0.4 vol% HF at 20 V for
2 h. The left-hand, middle, and right-hand images correspond to the top (a, d), bottom (b, e), and cross-sectional (c, f) views
of the NTs, respectively.

in diameter are clearly visible in the PNTs. Such partially
closed pores are not observed when RuO2 alone is doped into
the TiO2 NTs to form RuO2-doped TiO2 NTs (RNTs) [25], indi-
cating that the pore structure of the IRNTs originates from IrOx
deposition. As shown in the bottom views (Fig. 1b and e), the
IRNTs show smaller and more closely packed cells than the
PNTs, as has been previously observed when foreign compo-
nents are doped into TiO2 NTs. The IRNTs have a length of ca.
1.1 mm, which is longer than those of PNTs (ca. 0.8 mm) (Fig. 1c
and f) [29]. In a previous study [25], RNTs exhibited thicker

Fig. 2 e TEM-EDS mapping results for IRNTs prepared in 0.4 vol% HF. Ti, Ru, and Ir are marked as blue (b), red (c), and green
(d) spots, respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
6660 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 6 5 7 e6 6 6 4
films than those of PNTs due to the slow dissolution of the
RuO2-doped oxide films into the F
-containing solution.
Therefore, a thick film is formed due to the foreign elements,
such as IrOx and RuO2, in the TiO2 NTs. In addition, longer
IRNTs are expected from the equilibrium current density
during anodization, in which IRNTs show higher current
density than that of the PNTs (Supporting Information Fig. S4).
Interestingly, for IRNTs, Y-type (i.e., two NTs merged together)
or inverse Y-type (i.e., branched) NTs are often observed,
meaning that the electric field is non-uniformly distributed
over the NTs due to the dopants (Supporting Information
Fig. S5) [29]. The Y-type and inverse Y-type structures are
evidence of instability during NT growth, leading to the very
small, close-packed cells observed in the bottom view.
Fig. 3 e Length profiles of the IRNTs and histograms
showing the doping amount in the IRNTs, as revealed by
ICP-OES analysis. Fig. 3(a) and (b) shows the effects of HF
concentration and anodization time on the length of the
NTs (right Y-axis) and doping amounts (left Y-axis). A 0.4
vol% HF electrolyte was selected to investigate the effect of
anodization time on the length and amount of catalysts in
the IRNTs.
Fig. 2 shows the TEM and corresponding EDS analyses of
cross-sectional IRNTs, demonstrating that Ru and Ir are
evenly distributed over the entire body of the IRNTs. The
blue, red, and green spots (in the web version) correspond to
Ti, Ru, and Ir signals, respectively. It should be noted that the
amount of Ru as quantized by EDS is ca. twice that of Ir (1.12
and 0.52 at% for Ru and Ir, respectively). The EDS mapping of
the bottom side, where the doping of the two components as
well as TiO2 NT growth occur simultaneously, shows that the
amount of the catalysts is much higher than that shown
in the cross-sectional regimes (Supporting Information
Fig. S6). Ru and Ir are detected up to ca. 23 and 17%, respec-
tively, indicating that RuO2 is more doped into the NTs than
IrO2.
In order to more precisely assess the amount of catalysts in
the TiO2 NTs, the amount of Ru and Ir was quantized by ICP-
OES (Fig. 3). In contrast to the results from EDS analysis, the
amount of Ir is always higher than that of Ru, irrespective of
anodizing time and HF concentration. This is due to the fact
that ICP-OES measures the overall amount of catalyst,
including the surface-coating layer, whereas EDS shows only
local concentrations, especially inside the NTs. The sample
prepared in 0.3 vol% HF exhibits the highest amount of Ir and
the lowest amount of Ru (Fig. 3a). With a low concentration of
HF (0.3 vol%), which plays a role in the formation of NTs
during anodization, the NTs are not nucleated. Instead, a
barrier-type oxide is formed. However, TiO2 NTs are typically
formed in 0.3 vol% HF in the absence of IrOx precursors [9].
This discrepancy is due to electrostatic stabilization by metal
oxide NPs, in which the tiny particles are stabilized by
adsorbing anions (Cl
, OH
, and F
) from the solution onto
their surfaces [28,30‒32]. Consequently, NTs cannot be
nucleated due to the lack of free F
ions since the anions
participate in the stabilization of IrOx NPs in the electrolyte. In
addition, the negatively stabilized IrOx can be electrophoreti-
cally deposited on the barrier TiO2 films on which a positive
bias is applied. Since a large amount of IrOx is deposited
during the anodic bias, the competitor ion RuO4
is less
deposited, leading to a high amount of Ir and a low amount of
Ru on the barrier oxide film. As the HF concentration increases
up to the threshold concentration for NT formation, NTs
continuously grow perpendicular to the Ti substrate. Conse-
quently, diffusion of 2e3 nm IrOx particles through the narrow
NTs to the bottom of the NTs is relatively difficult, so they are
electrophoretically deposited at the top of NTs, forming the
partially closed pores (A in Fig. 1d). The IrOx deposits on the
top of the NTs are mainly composed of insoluble IrO2 and
soluble Ir2O3, which can generate IrO4
through reactions
(1)e(3) [33];
Ir2 O3 þ 3H2 O/2IrðOHÞ3 (1)
IrðOHÞ3 /IrO3 þ 3Hþ þ 3e (2)
IrO3 þ H2 O/IrO4
þ 2Hþ (3)



RuO4 and IrO4 diffuse to the bottom of the TiO2 NTs and
are simultaneously doped into the oxide films through the
following reactions [25];
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 6 5 7 e6 6 6 4 6661

Fig. 4 e XPS spectra of IRNTs prepared in 0.4 vol% HF at 20 V for 4 h shows the Ir4f (a), Ru3d (b), Ti2p (c), and O1s (d) spectra,
respectively. In the Ir4f and Ru3d spectra, peaks related to Ir2þ, Ir3þ, Ru2þ, and Ru4þ are presented after co-doping single-
step anodization.

Ti þ RuO4
/TiO2 þ RuO2 þ e (4)

Ti þ 1=2RuO4
þ H2 O/TiO2 þ 1=2RuO2 þ 2Hþ þ 5=2e (5)

Ti þ IrO4
/TiO2 þ IrO2 þ e (6)

Ti þ 1=2IrO4
/TiO2 þ 1=2IrO2 þ 2Hþ þ 5=2e (7)

Evidence for the selective dissolution of the Ir2O3 in IrOx

Fig. 5 e TEM image showing the morphology of IRNTs
annealed at 450  C. The SAED pattern was obtained on the
selected area indicated in the inserted image by the yellow
dashed square. The SAED pattern indicates polycrystallinity,
representing all the metal oxide phases in the NTs. (For
interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
can be indirectly observed by XPS analysis, and will be dis-
cussed in the section on XPS in detail. The average length of
the IRNTs prepared at 20 V for 2 h was measured as a function
of the HF concentration in the electrolyte. The NTs develop
successfully in electrolytes containing over 0.4 vol% HF, and
this concentration produces the longest NTs. The average
length of the NTs becomes shorter with increasing HF con-
centration. This can be ascribed to the fact that the dissolution
of the TiO2 NTs formed is faster in more concentrated HF.
The 0.4 vol% HF conditions were selected for further study
of the effects of anodization time on the length and doping
amounts of the IRNTs (Fig. 3b). Interestingly, a convex curve is
exhibited, showing that the IRNTs are shortest when anod-
ization is performed for 2 h. Currently, it is not clear why 2-h-
anodization affords the shortest IRNTs. However, from the
fact that the partially closed pores on the top of the NTs
(Fig. 1d) begin to be removed after 2 h, it can be speculated that
growth and dissolution of the NTs achieve steady-state con-
ditions after 2 h. This indicates that the formation of the
6662 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 6 5 7 e6 6 6 4

partially closed pores disturbs the formation of NTs until 2 h of
anodization, leading to the shortest NTs. Meanwhile, the
amounts of Ir and Ru in the TiO2 continuously increase as a
function of anodizing time (Fig. 3b), even though the length of
the NTs is almost the same as that at 1 h. This indicates that
the RuO2 and IrO2 accumulate due to the fact that both cata-
lysts are not easily dissolved in F
-based electrolytes.
The oxidation states of the metal oxides in the IRNTs and
PNTs prepared for 4 h were determined by XPS analysis (Fig. 4
and Supporting Information Table S1). The peaks at 61.6 eV in
the Ir4f spectra indicate that the main oxidation state of Ir is
If4þ, which corresponds to IrO2 [34]. Additionally, the Ir3þ peak
of Ir2O3 (62.3 eV) is revealed by peak deconvolution, whereas
only a Na2þ peak (62.6 eV) is detected for the PNTs, which
might originate from the NaOH electrolyte. From the fact that
the Ir3þ peak area decreases and the Ir4þ peak area increases
as anodization proceeds (Supporting Information Fig. S7), we
can deduce that the Ir2O3 component of the IrOx is selectively
dissolved. Note that since IrO2 is very stable in the electrolyte,
it cannot be easily dissolved under mild acidic conditions at
room temperature [35]. In the Ru3d spectra, Ru4þ (286.0 eV)
and Ru2þ (284.0 eV), related to RuO2 and RuOx, are found for
the IRNTs, whereas only a CO-related peak (285.0 eV) is
detected for the PNTs [36,37]. Upon introducing foreign metal
oxides into the TiO2, its Ti2p spectra are also slightly changed,
showing a new peak attributed to Ti3þ in Ti2O3 (457.2 eV).
Simultaneously, the peak in the hydroxide region of the O1s
spectra (531.5 eV) is intensified by the presence of Ru and Ir
oxides [38,39]. More detailed XPS information is shown in
Supporting Information Table S1. All the XPS data indicate
that even though the dominant oxide phases are IrO2, RuO2,
and TiO2, it is unavoidable that other oxide phases appear
because of the mismatch between rutile- and anatase-phase
oxides [40].
Transmission electron microscopy selected area electron
diffraction (TEM SAED) analysis was performed to provide
more specific crystallographic information, as shown in Fig. 5.
The ring patterns indicate that a polycrystalline phase is
formed on the IRNTs. The main rutile structures of RuO2 (200)
and IrO2 (101) are clearly defined and labeled with blue and
yellow dashed circles (in the web version), respectively. This is
in good agreement with a previous study [40], which
concluded that IrO2 and RuO2 alloys typically present poly-
crystalline structures. Thus, the TEM SAED analysis provides
convincing evidence that the binary metal oxide catalysts are
successfully doped into the TiO2 NTs.
Electrochemical characterization was performed to inves-
tigate the activities of the binary catalysts. From the LSV
(Fig. 6a and b), all the IRNTs exhibit remarkably low onset
potentials for the oxygen evolution reaction (OER), with the
catalysts prepared by anodization for 2 and 4 h showing onset
potentials lower than 1.0 V. The lowest onset potential of

Fig. 6 e The results of LSV for OER performance test (a and b, where b is a magnification of a) and (c) plot of O2 generation vs.
current density during the OER at 2.0 V. Analysis was conducted using O2 gas that gathered for single minute during OER in
0.1 M KOH solution, which was repeated ten times. (d) EIS measurement of samples. Note that the concentration of the
precursors is adjusted to 1 mM for all conditions, and anodization was carried out at 20 V for different times.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 6 5 7 e6 6 6 4
0.84 V (vs. SHE) is achieved by the IRNTs prepared for 4 h, and
is much lower than that of the PNTs (1.37 V). In addition, this
performance is maintained even after 50 cycles (Supporting
Information Fig. S8). The current densities at 2.0 V for the
IRNTs prepared for 1, 2, 4, and 8 h are 8, 53, 93, and
24 mA cm
2, respectively, indicating that there is an optimum
anodization time for the formation of IRNTs. The over-doping
of RueIr into the TiO2 NTs has a negative impact on OER ac-
tivity. The amount of O2 evolved over the IRNTs during the
OER at 2.0 V was measured by gas chromatography, revealing
that 230 mmol cm
2 min
1 of O2 gas is evolved for 1 min
(Supporting Information Table S2), which corresponds to a
faradaic efficiency of 99% (Fig. 6c). Current density vs. evolved
O2 gas shows a clearly linear relationship, demonstrating that
current density measurement during the OER is a suitable
indirect method for measuring OER activity. The current
density of 93 mA cm
2, obtained over the 4-h-anodized IRNT
prepared in this work, exceeds the previous result for a single
catalyst or multi-catalysts in the OER [41,42]. These excellent
electrocatalytic properties can be attributed to the low charge-
transfer resistance, which is confirmed by the Nyquist plot
obtained from electrochemical impedance spectroscopy
(Fig. 6d). Compared to the single-catalyst-doped NTs such as
INTs and RNTs, IRNTs present the smallest semicircle, indi-
cating that the alloying of Ru and Ir oxides has a synergistic
effect on electrocatalytic performance for the OER.
Conclusions
Single-step anodization for the simultaneous doping of binary
RuO2eIrO2 catalysts into TiO2 NTs was successfully achieved.
IrOx NPs and KRuO4 were successfully employed as precursors
for IrO2 and RuO2, respectively, and were doped into the TiO2
NTs with uniform distributions. When very low concentra-
tions of HF (0.3 vol%) were used during anodization, NT pores
were not created, and IrOx NPs were electrophoretically
deposited. As the concentration of HF increased, the length of
the NTs decreased due to the formed TiO2 being rapidly dis-
solved by HF. Interestingly, the concentration of binary cata-
lysts in the TiO2 NTs increased as a function of anodization
time, meaning that the catalysts were accumulated in the
TiO2 due to Ru and Ir being less soluble in HF. Through XPS and
TEM SAED analysis, the major oxidation states of the three
metals (Ru, Ir, and Ti) were revealed as Ru4þ, Ir4þ, and Ti4þ,
which corresponds to RuO2, IrO2, and TiO2, respectively. All
the metal oxides existed as polycrystalline phases because of
the presence of different crystalline phases such as rutile,
anatase, and other multiple oxide phases. In OER measure-
ments, the onset potential for the optimized IRNTs was
reduced to 0.84 V, which is much lower than that for the PNTs,
which exhibited an onset potential of 1.37 V. In addition, the
current density for 4-h-anodized IRNTs was ca. 93 mA cm
2 at
2.0 V, which is much higher than that measured for single-
catalyst-doped TiO2 NTs. Finally, we found that the amount
of evolved O2 (230 mmol cm
2 min
1, representing a faradaic
efficiency of 99%) and current density presented a linear
correlation. Moreover, the IRNTs exhibited excellent electro-
catalytic properties owing to their lower charge-transfer re-
sistances than those of INTs, RNTs, and PNTs.
6663
Notes
The authors declare no competing financial interest.
Acknowledgement
This research was supported by the Basic Science Research
Program through the National Research Foundation of Korea
(NRF), funded by the Ministry of Education (Grant number:
2015R1A4A1042434).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2016.12.018.
references
[1] Trasatti S. Electrocatalysis: understanding the success of
DSA. Electrochim Acta 2000;45:2377e85.
[2] Ferrara F. New Materials for eco-sustainable electrochemical
processes: oxygen evolution reaction at different electrode
materials [Ph.D. Dissertation]. France: University of Cagliari;
2008.
[3] Hoseinieh SM, Ashrafizadeh F, Maddahi MH. A comparative
investigation of the corrosion behavior of RuO2 e IrO2 e TiO2
coated titanium anodes in chloride solutions. J Electrochem
Soc 2010;157:E50e6.
[4] Cornell A, Håkansson B, Lindbergh G. Ruthenium based DSA
in chlorate electrolysis-critical anode potential and reaction
kinetics. Electrochim Acta 2003;48:473e81.
[5] Lee J, Jeong B, Ocon JD. Oxygen electrocatalysis in chemical
energy conversion and storage technologies. Curr Appl Phys
2013;13:309e21.
[6] Shin S, Choi Y-W, Choi J. Water splitting by dimensionally
stable anode prepared through micro-arc oxidation. Mater
Lett 2013;105:117e9.
[7] Lee K, Mazare A, Schmuki P. One-dimensional titanium
dioxide nanomaterials: nanotubes. Chem Rev
2014;114:9385e454.
[8] Roy P, Berger S, Schmuki P. TiO2 nanotubes: synthesis and
applications. Angew Chem Int Ed 2011;50:2904e39.
[9] Bauer S, Kleber S, Schmuki P. TiO2 nanotubes: tailoring the
geometry in H3PO4/HF electrolytes. Electrochem Commun
2006;8:1321e5.
[10] Sun X, Li Y. Synthesis and characterization of ion-
exchangeable titanate nanotubes. Chem Eur J
2003;9:2229e38.
[11] Wang YG, Zhang XG. Enhanced electrochemical capacitance
of NiO loaded on TiO2 nanotubes. J Electrochem Soc
2005;152:A671e6.
[12] Kim YJ, Chai SY, Lee WI. Control of TiO2 structures from
robust hollow microspheres to highly dispersible
nanoparticles in a tetrabutylammonium hydroxide solution.
Langmuir 2007;23:9567e71.
[13] Joo J, Kwon SG, Yu T, Cho M, Lee J, Yoon J, et al. Large-scale
synthesis of TiO2 nanorods via nonhydrolytic sol
gel ester
elimination reaction and their application to photocatalytic
inactivation of E. coli. J Phys Chem B 2005;109:15297e302.
6664 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 2 ( 2 0 1 7 ) 6 6 5 7 e6 6 6 4
[14] Cai Q, Paulose M, Varghese OK, Grimes CA. The effect of
electrolyte composition on the fabrication of self-organized
titanium oxide nanotube arrays by anodic oxidation. J Mater
Res 2005;20:230e6.
[15] Prakasam HE, Shankar K, Paulose M, Grimes CAA. New
benchmark for TiO2 nanotubes array growth by anodization.
J Phys Chem C 2007;111:7235e41.
[16] Yerokhin A, Nie X, Leyland A, Matthews A. Plasma electrolysis
for surface engineering. Surf Coat Technol 1999;122:73e93.
[17] Shin S, Kim K, Choi J. Fabrication of ruthenium-doped TiO2
electrodes by one-step anodization for electrolysis
applications. Electrochem Commun 2013;36:88e91.
[18] Mamaca N, Mayousse E, Arril-Clacens S, Napporn TW,
Servat K, Guillet N, et al. Electrochemical activity of
ruthenium and iridium based catalysts for oxygen evolution
reaction. Appl Catal B 2012;111:376e80.
[19] Wu Z, Wang Y, Sun L, Mao Y, Wang M, Lin C. An ultrasound-
assisted deposition of NiO nanoparticles on TiO2 nanotubes
arrays for enhanced photocatalytic activity. J Mater Chem A
2014;2:8223e9.
[20] Pozio A. Effect of low cobalt loading on TiO2 nanotube arrays
for water-splitting. Int J Electrochem 2014;2014:1e7.
[21] Angelinetta C, Trasatti S. Surface properties of RuO2 þ IrO2
mixed oxide electrodes. J Electroanal Chem 1986;214:535e46.
[22] Barison S, Daolio S, Fabrizio M, De Battisti A. Surface
chemistry study of RuO2/IrO2/TiO2 mixed-oxide electrodes.
Rapid Commun Mass Spectrom 2004;18:278e84.
[23] Lee K, Schmuki P. Ta doping for an enhanced efficiency of
TiO2 nanotube based dye-sensitized solar cells. Electrochem
Commun 2012;25:11e4.
[24] Hyang B, Yang W, Wen Y, Chan B, Chen R. Co3O4-modified
TiO2 nanotube arrays via atomic layer deposition for
improved visible-light photoelectrochemical performance.
ACS Appl Mater Interfaces 2015;7:422e31.
[25] Yoo H, Choi Y-W, Choi J. Ruthenium oxide-doped TiO2
nanotubes by single-step anodization for water-oxidation
applications. ChemCatChem 2015;7:643e7.
[26] Gim Y, Seong M, Choi Y-W, Choi J. RuO2-doping into high-
aspect-ratio anodic TiO2 nanotubes by electrochemical
potential shock for water oxidation. Electrochem Commun
2015;52:34e40.
[27] Kim S, Yoo H, Rhee O, Choi J. Doping of Pt into anodic TiO2
nanotubes for water oxidation: underpotential shock
method in Cl
solution. J Phys Chem C 2015;119:21497e503.
[28] Zhar Y, Hernandez-Pagan EA, Vargas-Barbosa NM, Dysart JL,
Mallouk TE. A high yield synthesis of ligand-free iridium
oxide nanoparticles with high electrocatalytic activity. J Phys
Chem Lett 2011;2:402e6.
[29] Steeves MM. Electronic transport properties of ruthenium
and ruthenium dioxide thin films [Ph.D. Dissertation]. The
University of Maine; 2011.
View publication stats
[30] Xu D, Diao P, Jin T, Wu Q, Liu X, Guo X, et al. Iridium oxide
nanoparticles and iridium/iridium oxide nanocomposites:
photochemical fabrication and application in catalytic
reduction of 4-nitrophenol. ACS Appl Mater Interfaces
2015;7:16738e49.
[31] Tso CP, Zhung CM, Shih YH, Tseng YM, Wu SC, Doong RA.
Stability of metal oxide nanoparticles in aqueous solutions.
Water Sci Technol 2010;61:127e33.
[32] Zhang Y, Chen Y, Westerhoff P, Hristovski K, Crittenden JC.
Stability of commercial metal oxide nanoparticles in water.
Water Res 2008;42:2204e12.
[33] Fabbri E, Habereder A, Waltar K, Ko € tz R, Schmidt TJ.
Developments and perspectives of oxide-based catalysts for
the oxygen evolution reaction. Catal Sci Technol
2014;4:3800e21.
[34] Pfeifer V, Jones TE, Velasco Velez JJ, Massue  C, Greiner MT,
Arrigo R, et al. The electronic structure of iridium oxide
electrodes active in water splitting. Phys Chem Chem Phys
2016;18:2292e6.
[35] Lee J, Kim Y. Chemical dissolution of iridium powder using
alkali fusion followed by high-temperature leaching. Mater
Trans 2011;52:2067e70.
[36] Paoli EA, Masini F, Frydendal R, Deiana D, Schlaup C,
Malizia M, et al. Oxygen evolution on well-characterized
mass-selected ru and RuO2 nanoparticles. Chem Sci
2015;6:190e6.
[37] Kim KS, Winograd N. X-ray photoelectron spectroscopic
studies of ruthenium-oxygen surfaces. J Catal
1974;35:66e72.
[38] Na€ slund LA, Sa
 nchez-Sa nchez CM, Ingason AS, Ba € ckstro
€ m J,
Herrero E, Rosen J, et al. The role of TiO2 doping on RuO2-
coated electrodes for the water oxidation reaction. J Phys
Chem C 2013;117:6126e35.
[39] Mazura M, Howind T, Gibson D, Kaczmarek D, Song S,
Wojcieszak D, et al. Investigation of structural, optical and
micro-mechanical properties of (NdyTi1
y)Ox thin films
deposited by magnetron sputtering. Mater Des
2015;85:377e88.
[40] Sardar K, Petrucco E, Hiley CI, Sharman JDB, Wells PP,
Russell AE, et al. Water-splitting electrocatalysis in acid
conditions using ruthenate-iridate pyrochlores. Angew
Chem Int Ed 2014;53:10960e4.
[41] Shilpa N, Manna J, Rajput P, Rana RK. Water oxidation
catalyst via heterogenization of iridium oxides on silica: a
polyamine-mediated route to achieve activity and stability.
ACS Catal 2016;6:5699e705.
[42] Ryu SY, Hoffmann MR. Mixed-metal semiconductor anodes
for electrochemical water splitting and reactive chlorine
species generation: implications for electrochemical
wastewater treatment. Catalysis 2016;6:59e74.