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Cite This: ACS Omega 2018, 3, 3429−3439

Effects of Anions and pH on the Stability of ZnO Nanorods for

Photoelectrochemical Water Splitting
Ching-Fang Liu, Yi-Jing Lu, and Chi-Chang Hu*
Department of Chemical Engineering, National Tsing Hua University, No. 101, Section 2, Kuang-Fu Road, Hsin-Chu 30013, Taiwan
*
S Supporting Information

ABSTRACT: This work demonstrates the improved stability

of zinc oxide nanorods (ZnO NRs) for the photoanode of
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solar water splitting under voltage biases by the addition of

borate or carbonate ions in the aqueous electrolyte with
suitable pH ranges. The ZnO NRs prepared by the
hydrothermal method are highly active and stable at pH 10.5
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in both borate and carbonate buffer solutions, where a

photocurrent higher than 99% of the initial value has been
preserved after 1 h polarization at 1.5 V (vs reversible
hydrogen electrode) under AM 1.5G. The optimal pH ranges
with a minimum morphological change of ZnO NRs for
photoelectrochemical (PEC) water splitting in borate and carbonate buffer solutions are 9−13 and 10−12, respectively. The
working pH range for PEC water splitting on ZnO NR photoanodes can be extended to 8.5−12.5 by the combination of borate
and carbonate anions. The lifetime of ZnO NR photoanodes can be synergistically prolonged for over an order of magnitude
when the electrolyte is the binary electrolyte consisting of borate and carbonate in comparison with these two anions used
individually. On the basis of the experimental results, a possible mechanism for the protective behavior of ZnO in borate and
carbonate solutions is proposed. These findings can be used to improve the lifetime of other high-performance ZnO-based
catalysts and to understand the photocorrosive and protective behaviors of ZnO NRs in the borate and carbonate solutions.

1. INTRODUCTION solution under ultraviolet illumination by hole trapping on its

Photoelectrochemical (PEC) water splitting has been consid-
ered a promising candidate for capture and high-capacity
storage of solar energy.1,2 A typical PEC cell generally consists
of a semiconductor photoelectrode in which electron−hole
pairs are generated upon light absorption. Following charge
carrier separation, electrons reduce water to hydrogen, while
holes oxidize water to oxygen. The ideal semiconductor
electrode used for water splitting would require the following:
(i) a suitable width of band gap >1.23 eV (thermodynamic
equilibrium voltage) +0.8 eV to overcome kinetic barriers; (ii)
the conduction band above the H+/H2 equilibrium potential for
hydrogen evolution and the valence band below the O2/H2O
equilibrium potential for oxygen evolution; and (iii) excellent
PEC and photocorrosion stability in aqueous solutions.3,4
Zinc oxide (ZnO) has attracted much attention in the past
decades as a favorable photoanode material toward achieving
efficient PEC water oxidation because of its good electron
mobility, excellent optical properties, wide availability, and low
toxicity.5,6 Recently, nanostructure engineering of ZnO films
has been shown to improve photocurrent yields because of the
large surface-to-volume ratio, which exhibits a great advantage
in the PEC water splitting for efficient delivery of photo-
generated carriers.7 Despite these excellent properties, ZnO-
based photoanodes are not commercialized to support reliable
and efficient PEC water splitting because of several limitations.
Most notably, ZnO suffers from photocorrosion in the aqueous
surface, which is a common problem for many other candidate
materials for water splitting.8 Another very serious issue is ZnO
decomposition when the solution pH values are too low or too
high, even in dark. From the potential−pH diagram of zinc in
water,9 the predominant dissolved zinc species in acidic to
neutral and basic media between 9.2 and 13.2 are Zn2+ and
Zn2+(OH)ii−, respectively. According to previous studies,8,10,11
ZnO was chemically dissolved in acids or strong bases under
potential biases and/or UV light illumination. Decomposition
of ZnO in aqueous solutions has been proposed as the
following reactions
ZnO(s) + 2H+ → Zn 2 + + H 2O (1)
ZnO(s) + H+ → ZnOH+ (2)
ZnO(s) + OH− + H 2O → Zn(OH)3− (3)
ZnO(s) + 2OH− + H 2O → Zn(OH)4 2 − (4)
The chemical dissolution corresponds to the direct reaction
of ZnO with protons and hydroxyl ions.10 The electrochemical
dissolution of ZnO generally needs an applied potential of
Received: February 4, 2018
Accepted: March 7, 2018
Published: March 23, 2018

© 2018 American Chemical Society 3429 DOI: 10.1021/acsomega.8b00214

ACS Omega 2018, 3, 3429−3439
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around 2 V versus standard hydrogen electrode (SHE).12
Accordingly, two competitive reactions for ZnO dissolution
were suggested13
2ZnO → 2Zn 2 + + O2 + 4e (5)
ZnO + 2H+ → ZnOH+ + H+ → Zn 2 + + H 2O (6)
However, the dissolution rate of ZnO under illumination is
faster than that under potential biases because of the addition
of chemical dissolution which depends on the concentration of
OH−. In fact, the dissolution rate of ZnO is a function of both
OH− and hole concentrations at the ZnO surface, which are a
function of both potential bias and light intensity.14 The
decomposition potential is determined by the formation of
dissolved products when the electrode has been photocorroded.
The equations describing the photoinduced decomposition of
ZnO are expressed as follows15
1
ZnO + 2p+ → Zn 2 + + O2
2 (7)
1
ZnO + 3OH− + 2p+ → HZnO2− + O2 + H 2O
2 (8)
1
ZnO + 4OH− + 2p+ → ZnO2 2 − + O2 + 2H 2O
2 (9)
Accordingly, the lowest solubility of ZnO is obtained at pH
9.3 (10−7 to 10 −8 M),16 and the solubility increases
exponentially when pH becomes lower or higher than 9.3.
Furthermore, Gerischer and Sorg17 proposed that the ZnO
dissolution rate depends on the type of anion in the solution,
which was directly proportional to the square root of the
electrode rotation speed, which is attributable to the diffusion
of protons.
To overcome these issues, two parallel paths are generally
employed: (i) development of new methods to improve the
stability of ZnO for the long-term usage in water splitting and
(ii) coatings of conductive and protective films to prevent
corrosion during the PEC reaction period.18 Recently, surface
modification of ZnO photoanodes, such as combination with
another semiconductor,19−23 deposition of noble metals,24 and
coupling with versatile carbon materials,25 has been proposed
to suppress the photocorrosion to provide the long-term
performance of ZnO electrodes for the water splitting process.
Moreover, phosphate and borate buffers have been shown to
enhance the rate of oxygen evolution and improve the stability
when various water oxidation catalysts such as manganese,26
cobalt,27 or nickel oxides28 were employed. By preventing the
accumulation of protons near the anode surface, these buffers
significantly increase the lifetime of the catalysts. Fekete et al.29
investigated the buffer effect on catalytic activity and stability of
ZnO in a 12 h stability test. They found that ZnO was
structurally stable in the borate buffer solution (pH 10.5) and
prolonged its lifetime during this PEC process. However, there
was no explanation for the impact of this buffered electrolyte on
the PEC stability of ZnO.
In this work, the influence of buffer electrolytes on the zinc
oxide nanorods (ZnO NRs) morphologies is investigated to
understand the buffer influences. The effects of pH in the
buffered electrolytes on the generation and stability of
photocurrent are discussed. The stability mechanism of ZnO
NRs and how to extend the pH window for improved stability
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of ZnO in the PEC water splitting process are proposed in this
study.
2. EXPERIMENTAL SECTION
2.1. Preparation of ZnO Electrodes. ZnO NRs on the
fluorine-doped tin oxide-coated glass slide (FTO glass, 7 Ω
sq−1) substrate were fabricated by a hydrothermal method
described in our previous study.30 A seed layer of ZnO was
deposited on FTO glass by spin-coating a solution of 10 mM
zinc acetate in ethanol and subsequent calcination at various
temperatures for 2.25 h to obtain the ZnO seed layer on FTO
glass. Then, the ZnO seed layer/FTO glass was transferred to a
50 mL Teflon-lined stainless steel autoclave containing 20 mM
Zn(NO3)2, 20 mM hexa-methylenetetramine, and 35 v/v %
polyethyleneimine aqueous solution for the hydrothermal
reaction at 98 °C for 4 h to obtain ZnO NRs on FTO glass.
ZnO NRs/FTO glass was rinsed with ethanol and deionized
water and finally dried in air at 80 °C.
2.2. Characterization of ZnO. Scanning electron micros-
copy (SEM) was performed with a HITACHI, SU8010 FESEM
instrument with an energy-dispersive X-ray spectroscopy
analysis system operated at 50 kV. X-ray diffraction (XRD)
patterns were obtained using Bruker APEX DUO. XRD
patterns were taken using Cu Kα as the radiation source with
a 1° divergence slit, 0.2° receiving slit, and carbon
monochromators at 1° min−1 (2θ range 20°−70°). Time-of-
flight secondary ion mass spectrometry (TOF-SIMS, Munich,
Germany) is used to characterize the surface composition of
the ZnO NRs on the FTO substrate. The primary ion source
was a pulsed 69Ga+ source (pulsing current 2.5 pA and a pulse
width of 30 ns) operated at 15 keV with a post-acceleration of
10 kV. The analysis area of 100 nm × 100 nm, data acquisition
time of 30 s, and charge compensation by applying low-energy
electrons (∼30 eV) from a pulsed flood gun were used for the
measurements. The mass resolution measured on the ZnO+/−
signal was m/Δm = 4000 in the positive and negative detection
modes. Calibration of the mass spectra in the positive detection
was based on the peaks such as H+ (1.007 m/z), B+ (11.0082
m/z), 64Zn+ (63.922 m/z), 66Zn+ (65.919 m/z), and in the
negative detection mode on C− (12.0004 m/z), O− (15.995 m/
z), CO2− (44.003 m/z), HCO2− (45.0118 m/z), 64ZnO−
(79.922 m/z), and 64ZnO− (81.9189 m/z).
2.3. (Photo)electrochemical Measurement. The PEC
catalytic activity of the ZnO NRs was tested by linear sweep
voltammetry (LSV) in a 0.5 M Na2SO4 solution (pH 6.8) using
a potentiostat (CH Instruments 4053a) under the three-
electrode mode. The ZnO NR photoelectrode, a Pt wire, and
an Ag/AgCl electrode were employed as the working, counter,
and reference electrodes, respectively. The LSV was measured
at 10 mV s−1 from −0.5 to 1.0 V versus Ag/AgCl in the positive
sweep direction. All PEC tests were measured under a 75 mW
cm−2 simulated sunlight source [a xenon lamp coupled with an
AM 1.5G filter (Newport)]. The measured potentials (vs Ag/
AgCl, 3 M KCl, Argenthal, 207 mV vs SHE at 24 °C) can be
transformed to be against the reversible hydrogen electrode
(RHE) according to the Nernst equation31
E RHE = EAg/AgCl + 0.0592pH + 0.207 (V) (10)
where ERHE is the transformed potential versus RHE.
Accordingly, ERHE = EAg/AgCl + 0.609 (V) because pH of the
0.5 M Na2SO4 solution is 6.8.
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Figure 1. (a) SEM surface and (b) cross-section images of ZnO NRs grown on the FTO substrate with the seed layer annealed at 330 °C for 135
min. (c) XRD patterns and (d) LSV curves of ZnO NRs on the FTO substrate with the seed layer annealed at (1) 300, (2) 330, and (3) 350 °C. The
LSV curves were measured in 0.5 M Na2SO4 at pH = 6.8 under the AM 1.5G simulated solar light irradiation.

Figure 2. (a) CA curves of a ZnO photoanode biased at 1.5 V vs RHE in (1,2) 0.5 M Na2SO4, (3) 0.5 M NaCl, (4) 0.5 M NaClO4, and (5) 0.025 M
Na2B4O7 with pH = (1) 6.8 and (2−5) 10.5. (b) CA curves of a ZnO photoanode biased at 1.5 V vs RHE in 0.025 M (1) Na2B4O7, (2) Na2CO3, (3)
glycine, and (4) Na2HPO4 with pH = 10.5 under the AM 1.5G simulated solar light irradiation.

Stability performance was tested in the electrolytes with pH
between 8.0 and 13.0. The electrolytes used were as follows: 0.5
M Na2SO4, 0.5 M NaCl, 0.5 M NaClO4, 0.025 M borate buffers
(at pH 8.0−13.0), 0.025 M carbonate buffers (at pH 9.0−
12.75), 0.05 M α-amino acetic acid (H2N−CH2−COOH, i.e.,
glycine), and 0.05 M phosphate buffer solution adjusted by 0.1
M NaOH and HCl solutions.
3. RESULTS AND DISCUSSION
3.1. Characterization of ZnO NRs. Figure 1a,b shows the
morphology of ZnO NRs grown on the FTO substrate, with an
average diameter and length of NRs equal to 70 nm and 1.38
μm, respectively. The crystal phase of ZnO NRs corresponds to
the standard XRD pattern of wurtzite ZnO (JCPDS card no.
36-1451) by powder XRD analysis (Figure 1c). Obviously, facet
(002) is the main peak for all samples. Facet (100) appears at
the seed layer annealing temperature equal to 330 °C, but its
intensity decreases with the increasing annealing temperature.
This result indicates that the c-axis orientation of ZnO gradually
increases with the annealing temperature.
3431
The PEC activity of ZnO NRs in 0.5 M Na2SO4 with pH =
6.8 was examined by LSV which reveals that the highest
photocurrent is 0.4 mA cm−2 when the ZnO seed layer has
been annealed at 330 °C (Figure 1d). This result is attributable
to the presence of the (100)-oriented ZnO NRs which provide
a superior carrier transport path along this direction and
provide a short pathway for minority carriers to reach the
interface.32 As a result, the PEC performance of these
nanostructured films is greatly improved. On the basis of the
abovementioned results and discussion, 330 °C is the seed-layer
annealing temperature of ZnO NRs used in the further studies.
3.2. Electrolyte Effects on the Stability of ZnO for PEC
Processes. Figure 2a compares the stability of ZnO NRs
biased at 1.5 V (vs RHE) in aqueous solutions containing 0.5 M
Na2SO4, 0.5 M NaCl, 0.5 M NaClO4, and 0.025 M Na2B4O7.
For the Na2SO4 solutions, the initial pH values were set at 6.8
and 10.5 (curves 1 and 2), while there was only one pH value
(10.5) for the other electrolytes (curves 3−5). Clearly, the
chronoamperogram (CA) curves in Figure 2a show significantly
different photocurrent responses of ZnO NRs in these
electrolytes, which is indicative of different PEC behaviors. In
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0.5 M Na2SO4 with pH = 6.8, the PEC activity of ZnO NRs

significantly decreases to 10% of the initial value within 30 min.
The declination in the photocurrent density is reduced when
the pH value is changed from 6.8 to 10.5 from a comparison of
curves 1 and 2. From the literature,33 the minimum solubility of
ZnO is between pH 9.9 and 12.3, which has been proposed to
be the stable operation pH window of ZnO. However, the PEC
activity of ZnO decays significantly within 20 min in that study.
Accordingly, the chemical dissolution of ZnO is expected to be
induced by the specific adsorption of certain anions on the
ZnO surface, and zinc complexes are liable to form in the Cl−-,
ClO4−-, and SO42−-containing solutions.33,34
From a comparison of curves 2−5, the stability of ZnO NRs
is very obviously improved in the Na2B4O7 electrolyte with pH
= 10.5. More than 100% of the initial photocurrent is preserved
after the 1 h PEC test. Clearly, anions are another important
factor influencing the stability of ZnO against photocorrosion.
A few studies indicated that the PEC stability of ZnO
photoanodes in the borate electrolyte is higher than that in
common electrolytes (e.g., SO42−) under the same pH.29
Because the borate ions with the buffering characteristics can
act as a proton/OH− donor and acceptor to compensate the
proton/OH− concentration gradient because of the heteroge-
neous reaction between photogenerated hole and water,35 the
localized pH value at the ZnO−liquid interface (i.e., interfacial Figure 3. SEM images of (a) freshly prepared ZnO NRs and (b−f)
pH) should not be significantly changed by the oxygen ZnO NRs after the 1 h CA test at 1.5 V vs RHE under the AM 1.5G
simulated solar light irradiation in (b) 0.5 M Na2SO4, (c) 0.025 M
evolution reaction (OER) or OH• formation. To confirm this
Na2B4O7, (d) 0.025 M Na2CO3, (e) 0.025 M glycine, and (f) 0.025 M
buffering effect on the stability of ZnO photoanodes, the PEC Na2HPO4 electrolytes at pH = 10.5.
stability of ZnO NRs was further tested in various buffer
electrolytes under AM 1.5G simulated solar light irradiation
(see Figure 2b). Clearly, the stability of ZnO NRs in the glycine Zn−glycine salts onto the ZnO NR surface in the glycine (an
and Na2HPO4 solutions is worse than that in the Na2B4O7 and organic acid containing the carboxylic group) solution, resulting
Na2CO3 electrolytes because the residual photocurrents in the in the decrease in the photocurrent (see Figure 3e), although
former two electrolytes are equal to 74 and 30% of the initial ZnO NRs are still visible after the PEC test. When the
values in the 1 h PEC test. In addition, more than 100% of the phosphate solution is employed, breakdown of ZnO NRs with a
initial photocurrent is preserved when the ZnO NR photo- passive film is visible from an examination of Figure 3f,
anode has been tested in the Na2CO3 solution for 1 h. probably resulting in the activity loss of ZnO NRs. From the
Accordingly, the mechanism for improving the PEC stability of literature,36 the formation of phosphates on the ZnO surface via
ZnO NRs cannot be simply attributed to the buffering effect of eq 11 is likely to adversely affect the PEC activity of ZnO
electrolytes, and the highest stability of ZnO can be obtained in
the Na2B4O7 and Na2CO3 electrolytes. Note that the order of Zn(OH)2 + Na 2HPO4 ↔ NaZnPO4 ·H 2O + NaOH
electrolytes with respect to decreasing the initial photocurrent (11)
is as follows: Na2B4O7 (0.59 mA cm−2) > Na2CO3 (0.55 mA Moreover, the maximum concentration of HPO42− species
cm−2) > Na2HPO4 (0.32 mA cm−2) > glycine (0.22 mA cm−2). was found in the pH range of 9 to 11.5, which could alter the
This interesting result implies that certain anions significantly dissolution process and form a passive layer of NaZnPO4·H2O
enhance the PEC activity of ZnO NRs, probably resulting from via eq 11.36 Because a tubular structure of ZnO is clearly found
the specific adsorption of these anions (see below). in Figure 3f, the crystal plane (002) of ZnO NRs has been
Typical SEM images of ZnO NRs before and after the 1 h corroded in the phosphate electrolyte. Because the above-
PEC test in various electrolytes are shown in Figure 3. In mentioned etching is selective, the positively charged Zn-
comparison with the fresh ZnO NRs shown in Figure 3a, the terminated [0001] polar surface of ZnO is believed to donate
diameter of ZnO NRs may be changed, depending on the Zn2+ to react with PO43− ions to form Zn3(PO4)2 as an
corrosion or salt deposition processes during the 1 h PEC test. insoluble salt which decreases its buffering capacity.37 There-
Because of the photocorrosion occurring in the Na2SO4 fore, the presence of phosphate ions promotes the selective
electrolyte, most ZnO NRs were dissolved from the FTO corrosion and declines the PEC activity of ZnO. On the basis of
glass substrate after the PEC test (see Figure 3b). On the other the abovementioned results and discussion, the PEC stability of
hand, the morphologies of ZnO NRs were not significantly ZnO can be improved by the usage of borate and carbonate
changed when ZnO NRs were tested in the Na2B4O7 and ions as the supporting electrolyte.
Na2CO3 electrolytes from a comparison of Figure 3a,c,d. These 3.3. pH Effects in the Borate and Carbonate Solutions
results reveal the improved PEC stability of ZnO in the on the Stability of ZnO NRs. To further investigate the
borate-/carbonate-containing electrolyte, and the adsorption of influence of the two abovementioned anions with buffering
these two anions may be under the monolayer situation. The characteristics on the stability of ZnO for PEC water splitting,
rough surface and large diameter of ZnO NRs in Figure 3e freshly prepared ZnO NR photoanodes were further tested in
indicate the significant photocorrosion and redeposition of the borate and carbonate solutions at various pH values, and
3432 DOI: 10.1021/acsomega.8b00214
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typical results are shown in Figures 4 and 5. The ZnO
photoanodes show excellent stability in the pH range of 9 to 13
Figure 4. CA curves of ZnO photoanodes biased at 1.5 V vs RHE in
0.025 M Na2B4O7 at pH = (1) 8.7, (2) 9.5, (3) 10.5, (4) 11.0, (5) 12.0,
and (6) 13.0 under the AM 1.5G simulated solar light irradiation.
Figure 5. SEM images of ZnO photoanodes after the 1 h CA test at
1.5 V vs RHE in 0.025 M Na2B4O7 at pH = (a) 8.7, (b) 9.5, (c) 10.5,
(d) 11.0, (e) 12.0, and (f) 13.0 under the AM 1.5G simulated solar
light irradiation.
(see Figure 4). Because of the buffering effect, these two anions
can release or capture protons to maintain the localized pH
value at the ZnO NR/electrolyte interface when the PEC water
splitting occurs.38 On the other hand, the interfacial pH should
decrease significantly during the PEC process when the
solution pH was adjusted to be lower than its pKa. Accordingly,
decay in the PEC activity of ZnO NRs is observed at pH = 8.7
which are lower than the pKa of Na2B4O7 (pKa1 = 9.23).
To evaluate the possible PEC activity decay mechanism, the
surface morphologies of ZnO NRs after the 1 h PEC test in the
Na2B4O7 electrolyte at various pH values are shown in Figure 5.
At pH = 8.7, almost all ZnO NRs have been dissolved into the
electrolyte, and the FTO substrate under the residual ZnO NRs
is clearly found in Figure 5a. When pH is 9.5, significant
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damages on the surface of ZnO NRs are visible, but their PEC
activity does not significantly decay in the 1 h PEC test from
Figure 4. Therefore, the damages on the surface of ZnO NRs
do not significantly destroy the [0001] facets such as (100) and
(002) which are the highly active sites for water splitting.32,39
At pH = 10.5, there is no change in the morphology of ZnO
NRs before and after the 1 h PEC test (Figure 5c), correlating
well with the high photocurrent stability over 1 h. At pH = 12,
12.5, and 13, ZnO NRs are slightly dissolved at the side of the
top surface. This result suggests that excess hydroxyl ions
adsorb preferentially onto the positively charged [0001]-Zn
surface to form the soluble zinc species, resulting in the increase
of the chemical dissolution rate when pH is higher than 12.3
(see Figure S1b−d).40 However, the PEC activity of ZnO NRs
does not significantly decay, illustrating that the (002) facet is
not significantly decomposed in the 1 h PEC test.
For the carbonate buffer electrolyte, good stability of ZnO
photoanodes is observed at pH between 10 and 12 (Figure 6).
Figure 6. CA curves of ZnO photoanodes biased at 1.5 V vs RHE in
0.025 M Na2CO3 at pH = (1) 9.0, (2) 9.5, (3) 10.5, (4) 11.0, (5) 12.0,
and (6) 12.5 under the AM 1.5G simulated solar light irradiation.
However, the PEC activity of ZnO decays when pH has been
increased to 12.5. Accordingly, the working pH range of ZnO
in the carbonate buffer electrolyte is narrower in comparison
with the borate buffer solution. Because the carbonate buffer
solution is highly effective for stable photocurrents when the
operation pH is closed to its pKa (ca. 10.2), the suitable
operation pH range for obtaining stable photocurrents of ZnO
should be shifted with the pKa value.
The morphologies of ZnO NRs after the 1 h PEC test in the
carbonate electrolyte at various pH values are shown in Figure
7a−f. Obviously, there is no visible change in the morphology
of ZnO NRs when pH is between 10 and 12. However, when
pH is increased to 12.5, a passive layer of Zn(OH)2(s) with
carbonate salts seems to be formed on the ZnO NR surface via
precipitation of saturated zincate ion [Zn(OH)42−], as shown in
Figure 7f.41 Therefore, the decay in the photocurrent of ZnO
NRs should reasonably result from the coverage of a passive
layer which reduces the photoconversion efficiency of ZnO
NRs in such an electrolyte. Although the photocatalytic activity
of ZnO for the OER can be promoted in alkaline solutions
because of an enhanced reaction rate between OH− and holes,
the dissolution of ZnO is also accelerated by the formation of
soluble zincate ions [Zn(OH)3−(aq) or Zn(OH)42−(aq) species]
in concentrated alkaline solutions via eqs 3 and 4.42,43 Hence,
the photocurrent density decreases when pH is higher than
10.5, implying that the rate of chemical dissolution (eqs 3 and
4) becomes significant. In contrast, the PEC activity of ZnO
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buffer-containing solutions should be diffusion-controlled by

the concentration of the buffer anion at pH lower than 12 and
by the OH− concentration at pH higher than 12. Interestingly,
the photocurrent of ZnO can be preserved at pH higher than
12 (see Figure 4); meanwhile, the morphology of ZnO NRs is
not significantly damaged after the 1 h PEC test (see Figure
5d−f). Dodd et al.49 reported that OH− could adsorb
preferentially onto the positively charged [0001]-Zn surface,
increasing the reaction rate between OH− and holes (i.e.,
accelerated water oxidation). This report suggests that the PEC
activity of ZnO to the OER or OH• formation is dependent on
its crystal facet. According to the abovementioned results and
discussion, the PEC activity and morphological change of ZnO
in pure NaOH solutions at various concentrations are worthy
of being investigated.
Figure 8a shows that the order of the NaOH concentration
with respect to decreasing the photocatalytic activity of ZnO is

Figure 7. SEM images of ZnO photoanodes after the 1 h CA test at

1.5 V vs RHE in 0.025 M Na2CO3 at pH = (a) 9.0, (b) 9.5, (c) 10.5,
(d) 11.0, (e) 12.0, and (f) 12.5 under the AM 1.5G simulated solar
light irradiation.

NRs can be preserved when the borate buffer electrolyte is

employed. This is probably due to the fact that the HBO32−
species existing at 12 < pH < 1444 are mainly responsible for
proton transport and reduce the concentration of hydroxyl ions
at the ZnO/electrolyte interface. Another possible reason is the
formation of the borate radical, •B(OH)4, (eqs 12−14), from
the oxidation of B(OH)4− by photogenerated holes at pH >
11.5, which might oxidize water and suppress the decom-
position of ZnO NRs.45,46
H3BO3 + H 2O ↔ [B(OH)4 ]− + H+ (12)
− •
[B(OH)4 ] ↔ [B(OH)4 ] + e (13)
•
[B(OH)4 ] ↔ •B(OH)3 O− + H+ (14)
We also investigated the effect of the anion concentration on
the stability of ZnO in the 1 h PEC test. Figures S2 and S3 Figure 8. (a) CA curves of ZnO photoanodes biased at 1.5 V vs RHE
show that the stability of ZnO NRs in a relatively low pH in (1) 0.001, (2) 0.01, (3) 0.1, (4) 0.2, and (5) 0.5 M NaOH. (b−e)
SEM images of ZnO photoanodes after the 1 h CA test at 1.5 V vs
solution can be improved by the increase in the anion
RHE in (b) 0.001, (c) 0.01, (d) 0.1, and (e) 0.5 M NaOH under the
concentration because of the stronger buffering capability.47 AM 1.5G simulated solar light irradiation.
However, the ZnO NRs have been found to be covered with
sodium zincate and zinc carbonate passive layers in borate (pH
8) and carbonate (pH 9.5) solutions (see Figure S4a,b). as follows: 0.1 M > 0.01 M > 0.001 M > 0.2 M > 0.5 M.
Because the XRD pattern of ZnO NRs with the 1 h PEC test at Surprisingly, the PEC activity of ZnO can be preserved in the
pH 8 in the borate buffer electrolyte confirms no obvious 0.1 M NaOH solution (pH ≈ 12.85). On the other hand, the
change in the crystalline wurtzite phase, the physicochemical photocurrent densities in such pure NaOH solutions are
properties of wurtzite ZnO NRs are retained, leading to the obviously lower than those obtained in the borate or carbonate
stable photocurrent (see Figure S4c). electrolytes, revealing the key role of the two abovementioned
On the basis the abovementioned results and discussion, the anions (probably via adsorption) in promoting the photo-
surface species formed from the reactions between anions and catalytic activity of ZnO. When the NaOH concentrations are
ZnO are dependent upon the solution pH, which are believed out of 0.01−0.1 M, the photocatalytic activity of ZnO NRs
to affect the resultant photocurrent density of ZnO NRs decays significantly where 20, 70, and 30% of the initial
obtained in the borate or carbonate solutions with different pH photocurrent can be respectively preserved in the 0.001, 0.2,
values. From the literature,48 the oxidation of ZnO in the and 0.5 M NaOH solutions after the 1 h PEC test. The
3434 DOI: 10.1021/acsomega.8b00214
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ACS Omega Article

abovementioned results indicate that the ZnO NR photoanode

is stable when the OH− concentration is between 0.01 and 0.1
M.
Figure 8b−e shows the morphologies of ZnO NRs after the 1
h PEC test in different NaOH solutions. Note that ZnO NRs
become thinner after the 1 h PEC test in 0.001 M NaOH (pH
≈ 10.95), as shown in Figure 8b, suggesting the dissolution of
ZnO NRs. Figure 8c,d shows no significant change in the
morphology of ZnO NRs when the ZnO photoanodes have
been tested in the 0.01 and 0.1 M NaOH media, although part
of ZnO NRs become slightly finer. Accordingly, the photo-
corrosion of ZnO slightly occurs in the two abovementioned
NaOH solutions. Also, note the visible dissolution on not only
the [0001] facet but also the nonpolar [101̅0] facet. This
phenomenon implies the homogeneous dissolution of ZnO
NRs, and the small diameter of NRs (<100 nm) limits the
dissolution of the top surface by a low diffusion rate.50 Because
the damage of the [0001] facet is minor in the 1 h PEC test, the
photocurrent of ZnO NRs can be preserved. However, when
the NaOH concentration reaches 0.2 M, ZnO NRs collapse, as
shown in Figure S5a. One possible reason is the formation of
passive Zn(OH)2(s) (see Figure S5b) via the precipitation of
saturated zincate [Zn(OH)42−] in the vicinity of the photo-
anode surface.41 Because of the coverage of such a passive layer
on the electrode surface, the [0001]̅ facet may be corroded
significantly by the damage of lattice oxygen via the
photodegradation according to the following reactions51
Figure 9. (1) Relative and (2) initial photocurrent densities of ZnO
+
ZnO + 2h → Zn 2+
+ O* (15) photoanodes biased at 1.5 V vs RHE in 0.025 M (a) Na2B4O7 and (b)
Na2CO3 at various pH values. The relative photocurrent density is the
O* + O* → O2 ratio between the initial photocurrent density and the photocurrent
(16)
density measured at time equal to 60 min.
In the 0.5 M NaOH solution, most ZnO NRs disappear and
the FTO substrate is exposed after the 1 h PEC test (see Figure the borate solution is above 0.1 M NaOH), the photocurrent
8e), revealing the serious damage of the ZnO NR photoanode. density of ZnO NRs is 0.46 mA cm−2, 30% higher than the
From all the abovementioned results and discussion, two photocurrent density obtained in 0.1 M NaOH (0.35 mA cm−2
possible mechanisms strongly depending on the pH value of from Figure 8a). In addition, the borate radical, •B(OH)4, can
electrolytes are proposed here to be responsible for the damage be formed in the aqueous solution at pH = 10.545,46 and might
of ZnO NRs. In the relatively low pH media (e.g., 0.001 M act as a mediator for hole transfer from ZnO to prevent the
NaOH), the diffusion-controlled dissolution of ZnO NRs occurrence of photocorrosion.
occurs. In the high pH solutions (e.g., 0.2 and 0.5 M NaOH), To further understand the protection behavior of ZnO in
facet-selective dissolution of ZnO NRs dominates because of borate and carbonate electrolytes, the surface composition of
the formation of a passive layer on ZnO NRs (i.e., eqs 15 and ZnO NRs was measured by TOF-SIMS in the positive and
16). negative modes. Figure 10 shows the intensity variation of
3.4. Possible Mechanism. The interactions among characteristic ions of ZnO (64Zn+ and 66Zn+), borate (B+), and
solution pH, buffer anion, and the PEC activity/stability of carbonate (CO2− and CHO2−) as a function of pH. From
ZnO NRs are shown in Figure 9a,b. When pH is lower than the Figure 10a, the intensity of characteristic ions of ZnO is close to
pKa value, the decay in the photocatalytic activity with the PEC 1 at the pH 9.5, 12, and 13, indicating that the construction of
testing time is attributable to the chemical dissolution (eqs 1 ZnO may not be changed after the 1 h PEC test. The intensities
and 2). With increasing pH, the PEC activity of ZnO is of 64Zn+ and 66Zn+ are increased when the pH is 8.7, indicating
enhanced by the adsorption of relatively concentrated OH− on a change in the chemical structure of the ZnO NR surface by
the active sites. In the meantime, the local pH at the vicinity of PEC corrosion. However, the decrease in the intensity of 64Zn+
the ZnO surface can be leveled by the buffering agents, and 66Zn+ is clearly found when pH is 10.5. This phenomenon
reducing the corrosion of ZnO by H+. Note that a stable is attributable to the adsorption of borate anions [B(OH)4−] on
photocurrent can be obtained in the borate buffer solution with the ZnO NR surface, as shown in Figure 10b. Such adsorbed
pH between 11 and 13 (see curve 1 in Figure 9a), but the borate ions reasonably act as a mediator for hole transfer from
photocurrent (i.e., PEC activity) reaches a maximum at pH = ZnO to promote the water oxidation and prevent the
10.5. The latter result reveals that the presence of borate ions occurrence of photocorrosion. In the carbonate electrolyte,
significantly promotes the PEC activity of ZnO, probably the intensities of characteristic ions of ZnO shown in Figure
because of the co-adsorption of borate and hydroxyl ions. The 10c are higher than 1, indicating that photocorrosion occurs
former result is also attributable to the co-adsorption of OH− when the solution pH is below 10. However, when pH is higher
and HBO32− on the ZnO surface, promoting the stability of than 12, a decrease in the intensity is found. Figure 10d shows
ZnO NRs. The abovementioned statements are supported by that the adsorption of carbonate ions results in the formation of
the fact that when pH equals 13 (i.e., the OH− concentration in the carbonate salt on the ZnO surface. As a result, the coverage
3435 DOI: 10.1021/acsomega.8b00214
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ACS Omega Article

Figure 10. Intensity of characteristic ions of (a,c) ZnO (64Zn+, 66Zn+), (b) boron (B+), and (d) carbonate (CO2− and CHO2−) for ZnO NRs after
the 1 h CA test at 1.5 V vs RHE under the AM 1.5G simulated solar light irradiation in 0.025 M (a) borate and (c) carbonate electrolytes as a
function of pH.

Figure 11. Schemes describe the photocorrosive and protective processes of ZnO NRs as a function of pH in the (a) borate and (b) carbonate
solutions.

of the carbonate salt can reduce the contact surface area
between ZnO and the electrolyte, leading to the decrease in the
PEC activity of ZnO, corresponding to Figure 9b. The presence
of carbonate ions in the borate electrolyte is reasonably
attributed to the dissolution of CO2(g) from the atmosphere.
On the basis of the literature41,45,46,52 as well as the
abovementioned results and discussion, the photocorrosive
and protective processes of ZnO as a function of pH in both
borate and carbonate buffer solutions are simply proposed as
the scheme shown in Figure 11. There are several key features
of the reaction scheme. First, the dissolution of zinc oxide is
attributable to both chemical and PEC reactions to form zinc
salt complexes on the electrode surface. Second, the buffering
agents can level the variations in H+ or OH− concentrations at
the electrode/electrolyte interface (e.g., the electrical double-
layer region) to maintain desired pH values to stabilize the
photoanode. Third, the adsorbed anions, for example, B(OH)4−
3436
or CO32−, can work as a hole mediator to promote the water
splitting reaction and suppress the photocorrosion. Fourth, the
formation of the zincate salt can protect the ZnO NRs but
results in the passivation of ZnO when the amount of carbonate
ions is too high in the high pH range (see Figure 11b). The
abovementioned phenomena should take place in the borate
and carbonate buffer solutions when their pH values are
significantly lower or higher than their respective pKa values.
To further confirm the idea that the stability of ZnO NRs can
be improved by the usage of borate and carbonate electrolytes
for the PEC water splitting, ZnO NR photoanodes were further
examined in the relatively long-term PEC test, and the
corresponding SEM images are shown in Figure S6. After the
12 h PEC test, the PEC activity of ZnO NRs decays slightly,
where 92 and 91% of the initial photocurrents can be preserved
in the borate and carbonate solutions, respectively. When the
PEC time was prolonged to 24 h, the photocurrents of ZnO
DOI: 10.1021/acsomega.8b00214
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NRs were found to decrease to 70 and 80% of their initial
photocurrents (see Figure S6a). Note that the morphologies of
ZnO NRs shown in Figure S6b,c were not significantly changed
after the 24 h-PEC test, which confirmed the improved stability
of ZnO NRs in the borate and carbonate electrolytes.
3.5. Stability of ZnO in the Binary Borate−Carbonate
Solution. Here, the combination of borate and carbonate
anions is proposed to improve the stability and PEC
performance of ZnO NRs in the solar water splitting process.
This idea is demonstrated by the PEC activity of ZnO NRs in
the mixed electrolyte with various pH values in the 1 h PEC
test. As shown in Figure 12a, curves 1 and 2 show that the most
Figure 12. (a) (1) Relative and (2) initial photocurrent densities of
ZnO photoanodes biased at 1.5 V vs RHE in 0.025 M Na2B4O7 +
Na2CO3 at various pH values. (b) Intensity of characteristic ions of (1)
B+, (2) CO32−, and (3) OH− for ZnO NRs after the 1 h CA test at 1.5
V vs RHE under the AM 1.5G simulated solar light irradiation in 0.025
M Na2B4O7 + Na2CO3 electrolytes as a function of pH.
stable photocurrent density (around 0.4−0.5 mA cm−2,
significantly larger than the maximum photocurrent density
obtained in the pure NaOH solution) can be obtained in the
mixed electrolyte with pH between 8.5 and 12.5. Accordingly,
the suitable and working pH range for ZnO in solar water
splitting is obviously extended by the combination of borate
and carbonate ions. When pH is lower than 8.5 or higher than
12.5, decay in the photocurrent has been found. Moreover, the
SIMS analysis of carbonate and borate anions from the ZnO
surface (curves 1 and 2 in Figure 12b) shows that the adsorbed
B+ and CO32− contents increase when pH is changed from 8.3
to 10.5. This result confirms that both borate and carbonate
anions can promote the PEC reaction. However, the adsorbed
CO32− and OH− contents (curve 3) increase when pH is
increased to 12.5, indicating that the adsorption of carbonate
ions results in the formation of the carbonate salt on the ZnO
surface. The highest intensity of OH− is found at pH 8.3 and
8.5 because of the formation of ZnOH+ on the ZnO NR surface
(eq 2). In addition, photocorrosive damage of ZnO NRs is also
visible in the abovementioned cases from Figure S7. Therefore,
the PEC activity and stability of ZnO can be improved by the
combination of Na2B4O7 and Na2CO3 buffering agents.
Table 1 compares the results of methods in suppressing the
photocorrosion of ZnO during the PEC reaction. Qiu et al.53
and Lee et al.54 reported the ∼90% loss of the initial
photocatalytic activity of ZnO-based photoanodes after a 1 h
test when a nonbuffered Na2SO4 electrolyte was used (pH 6.8).
The stability of ZnO was improved by doping metals into ZnO;
however, the decline of photocatalytic activity was observed
because of the dissolution of ZnO which contacted directly
between the partial bare ZnO electrode and the electrolyte.
Another improvement method is the TiO2 coating on ZnO,
which showed 100% stability. In comparison with the metal-
doped ZnO, the TiO2-coated ZnO shows completely preserved
photocurrent at pH 13 after the 1 h PEC reaction.55 However,
Yan et al.56 and Su et al.57 reported 86 and 90% retention of the
initial PEC activity in the nonbuffered Na2SO4 electrolyte using
BiVO4 and poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT) as
the protective films. Note that the electrical energy used by Yan
et al.56 was higher than that used in Liu et al.55 Note that
Fekete et al.29 has proposed that the stability of ZnO can be
improved by the usage of buffered electrolytes in the pH 9−
12.5 region. Also, note the ∼100% retention of the initial
photoactivity in the present study as well as the TiO2-coated
ZnO electrode reported by Liu et al.55 at pH 13. From a

Table 1. Stability Comparisons of ZnO-Based Photoanodes in Recent Literature

PCa retention after 1 h PEC
photo-anode electrolyte pH Eapp/initial j (%) refs
ZnO nanowire 0.1 M KOH 13 1.23 V vs RHE/0.4 mA cm−2 90 Liu et al.55
TiO2-coated ZnO nanowire 0.1 M KOH 13 1.23 V vs RHE/0.5 mA cm−2 100 Liu et al.55
PDMcT-coated ZnO NR arrays 0.5 M Na2SO4 6.8 1.15 V vs RHE/0.8 mA cm−2 90 (at 15 min) Su et al.57
ZnO NRs/BiVO4 0.5 M Na2SO4 6.8 1.8 V vs RHE/1.72 mA cm−2 86 (at 17 min) Yan et al.56
N-doped ZnO nanotetrapods 0.5 M Na2SO4 with phosphate buffer 7 1.0 V vs RHE/1.0 mA cm−2 90 Qiu et al.53
V-doped ZnO nanosheets 0.5 M Na2SO4 6.8 1.23 V vs RHE/17.12 μA cm−2 88 Lee et al.54
screen printed ZnO NPs 0.6 M borate buffer 10.5 1.23 V vs RHE/0.67 mA cm−2 100 Fekete et al.29
ZnO NRs 0.025 M borate buffer 10.5 1.5 V vs RHE/0.59 mA cm−2 100 this study
ZnO NRs 0.025 M carbonate buffer 10.5 1.5 V vs RHE/0.55 mA cm−2 100 this study
ZnO NRs 0.025 M borate buffer 13 1.5 V vs RHE/0.47 mA cm−2 93 this study
ZnO NRs 0.025 M borate + carbonate 8.5 1.5 V vs RHE/0.41 mA cm−2 100 this study

a
PC: photocurrent density under AM 1.5G simulated solar light irradiation.

3437 DOI: 10.1021/acsomega.8b00214

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ACS Omega
comparison of previous studies in the literature, Fekete et al.29
reported 100% stability after the 1 h PEC reaction at pH 10.5.
Nonetheless, our results are comparable to those reported by
these authors. In fact, the borate concentration used by Fekete
et al.29 is 24 times that employed in this study, although our
results are better than those reported by Fekete et al. This
result indicates that the stability of ZnO NRs in the binary
borate−carbonate electrolyte is better than that in the single
borate or carbonate electrolyte which is relatively easily
corroded by dissociation of Zn ions at relatively low pH
conditions (pH 8.5) during the reaction.
4. CONCLUSIONS
The ZnO NR photoanode is highly stable and active in the
PEC water splitting process when borate and carbonate ions
have been employed as the supporting electrolyte because their
buffering capability maintains the desired pH value at the
vicinity of the ZnO NR surface. The results of photocurrent
density and TOF-SIMS demonstrate that both anions adsorbed
on the ZnO NR surface can act as a mediator to increase the
photocatalytic activity of ZnO and protect ZnO NRs. The
working pH windows for the solutions containing single borate
or carbonate are equal to 9−13 and 10−12, respectively, where
more than 99% initial photocurrent can retain in the 1 h PEC
test. In the unsuitable pH conditions, the decrease in the PEC
activity of ZnO NRs is attributable to the photocorrosion of the
crystalline wurtzite phase. ZnO NRs are stable in the borate
and carbonate electrolytes at pH between 9.5 and 12 and show
a minor morphology change after the 1 h PEC test. When pH is
higher than 12.5, the photocatalytic activity decay of ZnO NRs
is dependent on the adsorption of buffer and hydroxyl ions in
the vicinity of the ZnO surface, resulting in the formation of a
passive Zn(OH)2 film with a carbonate salt layer, decreasing the
surface active sites. Most importantly, the stable working pH
window of ZnO in PEC water splitting is obviously extended
(between 8.5 and 12.5) by the combination of borate and
carbonate ions. The lifetime of ZnO photocatalysts for PEC
water splitting can be effectively prolonged using the binary
electrolyte.
■ ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsomega.8b00214.
Enlargement of the SEM images of ZnO photoanodes
after the 1 h PEC test in the borate buffer (Figure S1),
stability tests and properties of ZnO photoanodes in
different concentrations of borate and carbonate buffers
at different pH (Figures S2−S4), SEM image and
conceptual drawings associated with the working
mechanisms for ZnO NRs in the 1 h PEC test in 0.2
M NaOH (Figure S5), CA curves and SEM images of
ZnO NRs in borate and carbonate buffers in the 24 h
PEC test (Figure S6), and SEM images of ZnO
photoanodes after the 1 h PEC test in borate +
carbonate buffer (Figure S7) (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: cchu@che.nthu.edu.tw. Phone & Fax: +886-3-
5736027. Website: http://mx.nthu.edu.tw/?cchu/.
3438
Article
ORCID
Chi-Chang Hu: 0000-0002-4308-8474
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The financial support for this work, by Chang Chun Petro
Chemicals Co. Ltd., Chang Chun Plastics. Co. Ltd. and
Ministry of Science and Technology of ROC-Taiwan under
contract no. MOST 104-2622-8-007-001, is gratefully acknowl-
edged.
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DOI: 10.1021/acsomega.8b00214
ACS Omega 2018, 3, 3429−3439