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Decoupling half-reactions of electrolytic water

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Cite this: J. Mater. Chem. A, 2019, 7,

splitting by integrating a polyaniline electrode†
13149
Jianying Wang,a Lvlv Ji,b Xue Teng,a Yangyang Liu,a Lixia Guoa and Zuofeng Chen *a

Received 27th March 2019
Accepted 1st May 2019
DOI: 10.1039/c9ta03285a
rsc.li/materials-a
Conventional two-electrode water electrolyzers produce H2 accompanied by O2, and may suffer from gas
mixing and high cell voltage inputs. Herein, we introduce a low-cost conducting polymer material
polyaniline (PANI) as a solid-state redox mediator for decoupling the oxygen evolution reaction (OER)
and hydrogen evolution reaction (HER) in acidic media. It allows these two half-reactions to be
separated from each other in time during the electrolysis of water. As an intermediary material for
charge storage, the PANI electrode exhibits a remarkable reversible discharge capacity of 125 mA h g
1
at a current density of 0.2 A g
1. Moreover, an approach by controlling the equilibrium potential of the
PANI electrode is developed to balance the separate cell voltages. In this way, the decoupled HER and
OER can be sequentially driven at close cell voltages of only 0.8 V. Considering the low cost of PANI and
its excellent electrochemical performance, this study paves the way for the practical application of this
state-of-the-art decoupling strategy.

decouple the HER and OER.17,18 As a pioneering study in this

1. Introduction
Hydrogen is considered an ideal energy carrier because of its
high energy density and eco-friendly product (H2O).1–3 Water is
the largest reservoir of hydrogen and water splitting to produce
hydrogen can be driven, ideally by renewable-generated power
such as solar or wind.4–6 Electrochemical water splitting is
divided into two half-reactions: the oxygen evolution reaction
(OER) and the hydrogen evolution reaction (HER).7–9 In
conventional water splitting systems, these two half-reactions
occur simultaneously and the gas products H2 and O2 are
separated by using a proton exchange membrane.10–12 However,
such an electrolyzer conguration will greatly increase the mass
transfer resistance between the catalytic electrodes, especially
in the case of large current electrolysis.13 In addition, high-
pressure H2 and O2 gases produced in the individual compart-
ments may cross through the membrane to each other,
producing an explosive H2/O2 mixture.14,15 Consequently, a post-
process of purication is usually required to obtain pure H2 gas
for various applications, leading to an increase in economic
cost.16 To overcome these drawbacks, it is signicant to develop
a new strategy for decoupling water splitting half-reactions.
Recently, a new approach to avoid H2 and O2 mixing or to
obtain pure H2 gas of high economical value is to temporally
a
Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical
Science and Engineering, Tongji University, Shanghai 200092, China. E-mail:
zfchen@tongji.edu.cn
b
Key Laboratory of Advanced Textile Materials and Manufacturing Technology,
Zhejiang Sci-Tech University, Hangzhou 310018, China
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c9ta03285a
line of research, the concept of the electron-coupled proton
buffer (ECPB) was introduced by the Cronin group, whereby O2
and H2 can be produced at separate times during water elec-
trolysis by using redox mediators.19–21 This approach is
remarkable in contrast to spatially separated O2 and H2
production in a conventional electrolyzer. However, redox
mediators used in this study suffer from low capacity charge
storage because of their high molecular weights (H3Mo12PO40,
MW > 1800 g mol
1; H4SiW12O40, MW > 2800 g mol
1).19–21
Although the utilization of redox mediators such as small
organic molecules with good solubility in water may increase
the charge storage capacity, homogeneous molecules may
diffuse to the counterpart electrode followed by side reactions,
thus decreasing the coulombic efficiency.22,23 In this case,
a proton exchange membrane is still necessitated with impli-
cations for the durability and price of such devices.
To overcome this problem, Wang and Xia et al. recently
utilized Ni(OH)2/NiOOH as an inorganic solid-state redox
mediator to temporally decouple the HER and OER under
alkaline conditions.24,25 In the rst step, water reduction to
hydrogen occurs at the HER catalytic electrode which is
accompanied by the oxidation of Ni(OH)2 to NiOOH at the
intermediary electrode (Ni(OH)2 + OH

e
/ NiOOH + H2O).
In the second step, NiOOH is re-reduced to Ni(OH)2 (NiOOH +
H2O + e
/ Ni(OH)2 + OH
) by switching the polarity of the
power supply; with the stored charge released, water oxidation
to oxygen occurs at the OER catalytic electrode. As another solid
material of large family members, conducting polymers are
gaining increasing attention in the eld of energy storage and
conversion, because of their low cost and excellent chemical

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Journal of Materials Chemistry A
and physical properties that can be regulated by composition
and structure designing.26,27 For example, conducting polymers
have been proved to be very promising electrode materials for
batteries and capacitors. Conducting polymers used in elec-
trochemical energy storage usually have appropriate redox
potentials, good redox reversibility, and high capacity for
reserving charges. In this regard, conducting polymers may also
serve as ideal candidates of organic solid-state redox mediators
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for decoupled water splitting, enabling the decoupling strategy
to be more competitive.28,29
Herein, we introduce the application of low-cost polyaniline
(PANI) as a solid-state redox mediator for decoupling the HER
and OER in acidic media. As shown in Scheme 1, water splitting
to produce H2 and O2 can be decoupled into two sequential
steps driven by smaller cell voltages with redox equivalents
stored in PANI associated with ion doping/dedoping. The PANI
material exhibits reversible redox couples between the HER and
OER onsets, pointing to an excellent candidate for redox
mediators for the decoupling application. Due to its simple
structural units of low molecular weight and appropriate redox
potentials, the PANI electrode exhibits a high reversible
discharge capacity of 125 mA h g
1 at a current density of
0.2 A g
1 for decoupling the HER and OER. Moreover, by opti-
mizing the redox state of the PANI electrode, the decoupled
HER and OER can be sequentially driven by balanced cell volt-
ages down to 0.8 V. Compared with the conventional electro-
lyzer, the high voltage required for overall water splitting
reaction is divided into two close low voltages for the decoupled
HER and OER.
2. Results and discussion
The PANI powder was facilely synthesized by chemical oxidation
polymerization of aniline (ANI) monomers with ammonium
peroxodisulfate (APS) as the oxidant agent and MnO2 as the
initiator in 1 M HCl in an ice water bath under stirring.30 A
detailed procedure of the synthesis is presented in the
Scheme 1 A schematic illustration of the operation process for
decoupling water splitting. The H2 production process involves proton
reduction at the HER electrocatalytic electrode accompanied by
oxidation of the reduction-state PANI (r-PANI, dedoped) electrode.
The O2 production process involves H2O oxidation at the OER elec-
trocatalytic electrode accompanied by reduction of the oxidation-
state PANI (o-PANI, doped) electrode.
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Experimental section in the ESI.† Note that for better mixing,
the conductive agent carbon black was added into the reaction
solution during the polymerization of aniline. The results of
characterization in Fig. S1–S5† indicate that the as-synthesized
PANI is in the form of a dark green powder, which is of poor
crystallinity with a loose, layered structure. To prepare the PANI
lm electrode, the PANI powder was then pressed onto a Ti-
mesh at a pressure of 10 MPa for 2 minutes.
To achieve efficient water splitting in a conventional elec-
trolyzer, a practical voltage $ 1.6 V is usually required, con-
sisting of the theoretical decomposition voltage (1.23 V) and the
unavoidable overpotential (>300 mV).31,32 At present, most of the
single solar cells and alkaline dry cells cannot meet this large
voltage requirement and directly drive the water splitting.33,34 In
the decoupled water splitting process, however, the single-step
large power input may be fullled by two-step small power
inputs, making the water splitting reactions match better with
the existing power supplies.
As shown in Fig. 1A, the difference (DE ¼ 1.23 V) between the
theoretical onset potentials of the HER and OER represents the
minimum voltage required for the overall water splitting. In the
decoupling conguration, this voltage can be rationally divided
and applied sequentially to the HER and OER half-reactions,
with the aid of the intermediary electrode as the redox medi-
ator (note Scheme 1). The cell voltage required for the individual
HER (DE1) and OER (DE2) is dependent on the potential of the
redox mediator. Ideally, DE1 z DE2 could be realized when the
potential of the redox mediator is located in the middle of HER
and OER onsets. As a result, the same power source of small
voltages can be applied to sequentially drive the HER and OER,
strengthening the merit of the decoupling strategy. In this
regard, the development of redox mediators with an appropriate
redox potential is the key to balance the two power inputs. In
literature reports, although a few redox mediators have been
explored for the decoupling strategy, the individual voltages
applied for the decoupled HER and OER have not been well
balanced and a high voltage > 1.23 V is still required for at least
one half-reaction.19–21
The electrochemical performance of the PANI material was
rst investigated in 0.5 M H2SO4 solution using a typical three-
electrode setup. Fig. 1B shows the cyclic voltammogram (CV)
Fig. 1 (A) The voltage requirements for redox mediator-assisted water
splitting. DE is the theoretical voltage required in the conventional
water splitting system; DE1 and DE2 are voltages required for the
decoupled HER and OER by using a redox mediator. (B) CV curve of
the PANI film electrode, and LSV curves of the Pt electrode for the HER
and the RuO2/IrO2 electrode for the OER at a scan rate of 10 mV s
1.
This journal is © The Royal Society of Chemistry 2019

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curve of the PANI lm electrode, along with the linear scan
voltammogram (LSV) curves of the Pt electrode for the HER and
the commercial RuO2/IrO2 electrode for the OER. The CV curve
of PANI displays two characteristic redox couples, which are
attributed to the transitions between different doping states of
PANI, namely leucoemeraldine–emeraldine (E1/2 ¼ 0.39 V) and
emeraldine–pernigraniline (0.85 V) coupled with loss and gain
of electrons on PANI.35 The redox couples of PANI are located
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between the HER and OER onsets, indicating that PANI can be
used as a redox mediator to decouple the water splitting.23 The
good symmetry of the redox waves indicates the high electro-
chemical reversibility of the PANI electrode.
The kinetics of the PANI lm electrode was investigated by
CV measurements at scan rates from 20 mV s
1 to 100 mV s
1 in
0.5 M H2SO4. As shown in Fig. 2A, the peak current of the anodic
wave varies linearly with the square root of the scan rate. This
indicates a diffusion-controlled doping/dedoping process of the
PANI electrode that is related to the diffusion process of H+
inside the solid-state PANI electrode. The kinetics of the elec-
trode process was also analyzed via electrochemical impedance
spectroscopy (EIS) measurements and the EIS plot is shown in
Fig. 2B. The intercept of the EIS curve with the X-axis represents
an internal resistance of Rs ¼ 10 U for the system. In the high-
frequency domain, the EIS curve features a small semicircle,
indicating a small charge transfer resistance of Rct ¼ 7.5 U for
the redox reaction of emeraldine/pernigraniline.35 In addition,
a linear curve was observed in the low-frequency domain of the
EIS curve, consistent with the diffusion-controlled kinetics of
the doping/dedoping process of the PANI electrode.
The effectiveness of PANI as a redox mediator was then eval-
uated by examining the cell voltages required to deliver a given
current density for the decoupled water splitting. Fig. 3A shows
the reductive LSVs of the Pt electrode and PANI electrode in
a three-electrode system in 0.5 M H2SO4. The proton reduction to
H2 at the Pt electrode and reduction of the PANI electrode require
a bias of
0.08 V and 0.56 V, respectively, to reach a current
density of 50 mA cm
2. Correspondingly, Fig. 3B shows that the
PANI electrode can deliver an oxidative current density of 50 mA
cm
2 at 0.75 V, whereas water oxidation to O2 at the RuO2/IrO2
electrode requires 1.65 V to achieve the same current density.
Fig. 2 (A) CVs of the PANI film electrode at scan rates from 20 to
100 mV s
1 with an increment of 20 mV s
1 and plot of the anodic peak
current at 0.52 V versus the square root of the scan rate. (B) EIS of the
PANI film electrode at the open circuit potential. Inset: the corre-
sponding equivalent circuit diagram.
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Fig. 3 (A) LSVs for proton reduction to H2 at the Pt electrode and
reduction of the PANI electrode. (B) LSVs for water oxidation to O2 at
the RuO2/IrO2 electrode and oxidation of the PANI electrode. (C)
Galvanostatic charge–discharge and (D) cycling stability curves of the
PANI electrode at a current density of 0.2 A g
1.
Based on the above data, we analyse the cell voltages
required to produce a given current density of 50 mA cm
2
during the decoupled water splitting. For the OER with the
electrode pair RuO2/IrO2kPANI, it requires a cell voltage of 1.09
(¼1.65
0.56) V to oxidize water to oxygen, which is accom-
panied by reduction of the PANI electrode. Correspondingly, for
the HER with the electrode pair PANIkPt, it requires a cell
voltage of 0.83 (0.75
(
0.08)) V to reach the same current
density by reduction of protons to H2 and re-oxidation of PANI.
This gives an overall voltage requirement of 1.92 (¼1.09 +
0.83) V in the decoupled two-step process. This value is only
slightly higher than 1.73 (¼1.65
(
0.08)) V required for the
conventional RuO2/IrO2kPt electrolyzer due to the internal
resistance of the intermediary PANI electrode.19,22 Moreover,
because the decoupled water splitting by using PANI can be
achieved with two-step power inputs, it potentially allows the
renewable-generated power of lower voltages to be directly
employed for water splitting.
The charge storage capacity of the PANI lm electrode was
measured by galvanostatic charge–discharge tests in 0.5 M
H2SO4. As shown in Fig. 3C, it exhibits a reversible discharge
capacity of 125 mA h g
1 at a current density of 0.2 A g
1 in the
potential range from 0.1 to 1.2 V, which is higher than that of
the soluble phosphomolybdic acid (27.6 mA h g
1) or silico-
tungstic acid (18.6 mA h g
1) and the solid-state poly-
triphenylamine (77 mA h g
1) as redox mediators.19,20 The high
capacity of PANI is attributed to the multiple redox processes,
and the wide redox potential window, as well as the simple
structural units of low molecular weight. We also conducted the
charge–discharge measurement on the PANI electrode at higher
rates. As shown in Fig. S6,† a reversible capacity of 53 mA h g
1
can still be achieved at a high rate of 5 A g
1, indicating the high
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Journal of Materials Chemistry A
reversibility of the PANI electrode. The stability of the PANI
electrode was tested at a charge–discharge rate of 0.2 A g
1. As
shown in Fig. 3D and Fig. S7,† the PANI electrode displays an
excellent coulombic efficiency around 100% during 40 cycles
with capacity retention about 92%.
Aer establishing the energetics and capacity of PANI as
a redox mediator using the standard three-electrode setup, we
explore possibility of using it to decouple electrolytic water
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splitting. As demonstrated in Fig. S8,† the decoupled electro-
lyzer setup is constructed with a commercial RuO2/IrO2-coated
Ti-mesh electrode for the OER (le), a PANI lm electrode as the
solid-state redox mediator (middle), and a commercial Pt-
coated Ti-mesh electrode for the HER (right). The whole elec-
trolyzer setup is designated as RuO2/IrO2kPANIkPt. The equi-
librium potential is an important feature for the PANI material,
which is dependent on its charge–discharge state. Fig. 4A and B
show that the applied voltages for triggering the HER and OER
are closely associated with the equilibrium potential of the PANI
electrode. By increasing the equilibrium potential of PANI from
0.4 V to 0.8 V, the applied voltage for the OER onset is
decreased, while this value for the HER onset changes oppo-
sitely. At an equilibrium potential of 0.7 V, the decoupled HER
and OER can be driven at close voltages of only 0.75 V. We note
that it is important to get the cell voltage balanced during the
decoupled water splitting, which has the benet of utilizing the
same power supply for both OER and HER by simply switching
the power polarity.
The decoupled water splitting performance was also inves-
tigated by chronopotentiometry measurements. As shown in
Fig. 4C, at a PANI equilibrium potential of 0.4 V, it requires a cell
voltage of 0.55 V for reaching an HER current of 5 mA
Fig. 4 (A) LSVs for the decoupled water splitting with PANIkPt for the
HER and RuO2/IrO2kPANI for the OER. (B) Cell voltages for the
decoupled HER and OER onsets in (A). (C) Chronopotentiometric
curves for the decoupled HER and OER at 5 mA (0.025 A g
1) with the
PANI electrode at equilibrium potentials of 0.4 V and 0.7 V. (D)
Decoupled OER and (E) HER driven by a commercial Si solar cell.
13152 | J. Mater. Chem. A, 2019, 7, 13149–13153
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(0.025 A g
1) at PANIkPt and 1.32 V for the OER at RuO2/IrO2-
kPANI. In contrast, by increasing the equilibrium potential of
PANI to 0.7 V, the HER and OER processes require close cell
voltages of 0.8 V to reach the same current. This result indicates
further that the applied voltage for the decoupled HER and OER
can be regulated by controlling the equilibrium potential of
PANI. Consequently, the overall water splitting can be realized
with a power supply of only 0.8 V by two-step inputs. Such
balanced, low cell voltages for decoupling water splitting have
not been achieved in earlier studies.23
To examine the practicability of the system, a commercial Si
solar cell of 1.0 V under natural sunshine was employed as the
power source to decouple the OER and HER using RuO2/IrO2-
kPANIkPt. With the assistance of the PANI electrode, the inter-
mediary electrode can store protons and electrons generated
during the OER process and release protons and electrons
during the HER process. As shown in Fig. 4D, E and S9,† the
OER and HER processes can be sequentially driven by the solar
cell, as evidenced by vigorous gas bubbles at both RuO2/IrO2
and Pt electrodes. By contrast, in the absence of the interme-
diary PANI electrode, water splitting is hardly achieved by
a commercial alkaline zinc-manganese dioxide dry battery of
1.5 V by simply combining the RuO2/IrO2 anode and Pt
cathode (RuO2/IrO2kPt), as shown in Fig. S10.†
The decoupled HER and OER can also be carried out
concurrently in separate compartments with the assistance of
the intermediary PANI electrodes, as shown in Fig. S11.† In this
conguration, the oxidative and reductive equivalents were
stored in different PANI electrodes, respectively. Aer the PANI
electrode in the cathode compartment is oxidized and the PANI
electrode in the anode compartment is reduced, the two solid-
state intermediary electrodes can be exchanged between the
cathode and anode compartments that reverses the reactions in
these two intermediary electrodes. As shown by the chro-
nopotentiometric curves in Fig. S11D,† this implementation
allows the decoupled HER and OER to occur concurrently and
continuously in separate compartments during the electrolysis
of water.24
3. Conclusions
In summary, we introduce a low-cost polyaniline electrode as
a solid-state redox mediator for decoupling H2 and O2 produc-
tion in acidic water electrolysis. The polyaniline electrode
exhibits a reversible discharge capacity of 125 mA h g
1 at
a current density of 0.2 A g
1. In addition, by simply regulating
the equilibrium potential of the PANI redox mediator, the
decoupled HER and OER can be sequentially driven by cell
voltages of only 0.8 V, conquering the single high voltage
required for the overall water splitting reaction in the conven-
tional electrolyzer. The features of PANI as the redox mediator
are remarkable and should lead to more convenient and
competitive routes for decoupling production of renewable
fuels of high purity. Along this line, earlier studies on PANI as
the electrode material for batteries and capacitors would be of
great help for further development of the PANI-decoupled water
splitting system.
This journal is © The Royal Society of Chemistry 2019

Paper
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21573160 and 21872105), the Funda-
Published on 01 May 2019. Downloaded by Australian National University on 2/12/2020 5:35:38 AM.
mental Research Funds for the Central Universities, and the
Science & Technology Commission of Shanghai Municipality
(14DZ2261100).
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