Li2020 Article WaterSplittingFromElectrodeToG

ISSN 2311-6706
e-ISSN 2150-5551
CN 31-2103/TB
REVIEW https://doi.org/10.1007/s40820-020-00469-3
Water Splitting: From Electrode to Green Energy

System
Cite as
Nano-Micro Lett.
(2020) 12:131 Xiao Li1, Lili Zhao1, Jiayuan Yu1, Xiaoyan Liu1, Xiaoli Zhang3, Hong Liu1,2 *,
Weijia Zhou1 *
Received: 6 April 2020
Accepted: 21 May 2020
© The Author(s) 2020 Xiao Li, Lili Zhao and Jiayuan Yu contributed equally to this work.
* Hong Liu, [email protected]; Weijia Zhou, [email protected]

1
Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy
in Universities of Shandong, Institute for Advanced Interdisciplinary Research (iAIR), University of Jinan,
Jinan 250022, People’s Republic of China
2
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, People’s Republic of China
3
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001,
People’s Republic of China
HIGHLIGHTS
• Bifunctional electrode and electrolytic cell configuration for electrochemical water splitting are reviewed.
• The different green energy systems powered water splitting are summarized and discussed.
• An outlook of future research prospects for the development of green energy system powered water splitting in practical application
process is proposed.
ABSTRACT Hydrogen (H2) production is a latent feasibility of renewable clean energy.

2 production is obtained from reforming of natural gas, which consumes
The industrial H _
NF
+
NFO2
a large amount of nonrenewable energy and simultaneously produces greenhouse gas

H2
Photoelectrochemical NiFeSP
Hematite
cell
carbon dioxide. Electrochemical water splitting is a promising approach for the H2 pro-
H2
Au
Solar cells device Spiro
O2 Perovskite
duction, which is sustainable and pollution-free. Therefore, developing efficient and layer
TiO2
TiO2 blocking
FTO
Pt
economic technologies for electrochemical water splitting has been an important goal for Thermoelectric generator
Water splitting
Glass
Thermoelectric device Photoeletrode device
researchers around the world. The utilization of green energy systems to reduce overall driven by green
Water driven energy systems
energy consumption is more important for H2 production. Harvesting and converting
TENG
1000 µF
H2 O2
KOH
energy from the environment by different green energy systems for water splitting can FR4 Copper Kapton Gold
efficiently decrease the external power consumption. A variety of green energy sys- Triboelectric
nanogenerator
ΔT
+ _
Electric energy
device
device
tems for efficient producing H2, such as two-electrode electrolysis of water, water split- Surface charges
ΔT
ΔPs
ting driven by photoelectrode devices, solar cells, thermoelectric devices, triboelectric

Surface charges
PZT sheet O2 H2
Pyroelectric device
nanogenerator, pyroelectric device or electrochemical water–gas shift device, have been

developed recently. In this review, some notable progress made in the different green energy cells for water splitting is discussed in detail.
We hoped this review can guide people to pay more attention to the development of green energy system to generate pollution-free H
2
energy, which will realize the whole process of H2 production with low cost, pollution-free and energy sustainability conversion.
KEYWORDS Water splitting; Electrode; Green energy system; Renewable energy; Hydrogen production
Vol.:(0123456789)
13
131 Page 2 of 29 Nano-Micro Lett. (2020) 12:131
1 Introduction device, TENG and other devices including pyroelectric and

water–gas shift (WGS) reaction and so on (Fig. 1). These
With the gradual intensity of global energy crisis, hydrogen green energy systems can efficient drive water splitting for
(H2) is one of the most sustainable and clean energies for H2 production. Some notable matters and challenge in the
replacing fossil fuel energy [1, 2]. Reforming natural gas different green energy system for water splitting are dis-
to produce H2 not only consumes a large amount of natural cussed in detail in this review.
resources but also produces undesired carbon dioxide, which
causes greenhouse effect [3–5]. Splitting water into H2 and 2 Two‑Electrode Electrolysis of Water
oxygen (O2) was from more than 200 years ago. It is very
important to develop an environmental-friendly and low-cost Electrochemical water splitting is a prospective method to
technology for large-scale production of H2 [6]. As a mature produce environmentally friendly hydrogen fuel [18]. Elec-
energy conversion technology, electrolysis of water provides trochemical water splitting requires a voltage of 1.23 V in
a simple, efficient and promising method for the hydrogen theory; however, over 1.8 V is needed in practice to over-
evolution reaction (HER) [7–10]. However, an external come the activation barrier of the reaction [19]. The large
power supply to deliver oxidation or reduction reactions of overpotential is from the slow four-electron transfer kinetics
H2O is necessary for electrolysis, leading to economically of the anodic oxidation reaction and the easy two-electron
inefficient application of energy. Alternatively, harvesting, transfer kinetics of the cathode reduction reaction [20, 21].
storing and converting energy from the environment (such In addition, it is difficult to establish a water splitting system
as wind, thermal, sunlight, tidal and self-powdered energy) of different cathode and anode because different catalysts are
[11, 12] can be directly utilized for electrolysis with using a active and stable in different pH ranges. Moreover, the use of
lower or no external power supply. different catalysts in the same system often needs different
Sunlight is an inexhaustible renewable energy source equipment and methods, which increases the complicacy and
that can meet humanity’s needs. Effective utilization of cost of the system. And also, the wettability of the electro-
solar energy can reduce the overall energy consumption of catalyst with electrolyte and the rapid desorption of bubbles
water splitting [13, 14]. For example, constructing a photo- generated on the electrodes are very important in the process
electrode to absorb sunlight can provide a photovoltage to
effectively reduce the external energy supply for electrolysis
of water [15, 16]. In addition, solar cell is also an effective
technology of solar energy conversion, which can directly
absorb sunlight to transform output voltage instead of exter- _
NF
+
NFO2
nal electric energy, thus effectively realizing the minimum of H2
NiFeSP
external energy consumption. The utilization of heat energy
Photoelectrochemical
Hematite
cell
H2
Au
from sunlight in nature for thermoelectric (TE) device can O2

Solar cells device Spiro
Perovskite
generate power to provide the voltage of water splitting TiO2

TiO2 blocking
layer Pt
FTO
[17]. There are also vast amount of wind and tidal energy in Glass
Water splitting
Thermoelectric generator
nature, which can be captured by triboelectric nanogenerator Thermoelectric device

driven by green
Photoeletrode device
(TENG) to generate electricity, which can also effectively Water driven energy systems
TENG
reduce the input of external energy. Therefore, it is of great 1000 µF

H2 O2
significance to establish a suitable externally driven sys-

KOH
tem of water splitting to reduce external consumption and

FR4 Copper Kapton Gold
Triboelectric Electric energy

improve H2 production capacity.
ΔT
nanogenerator + _
device
device
For the past few years, many researchers have devel- Surface charges
ΔT
oped a variety of green energy system for efficient produc-

ΔPs
Surface charges
PZT sheet O2 H2
Pyroelectric device
ing H2, such as two-electrode electrolysis of water, water
splitting driven by a photoelectrode device, solar cells, TE
Fig. 1 Water splitting driven by different green energy systems
© The authors https://doi.org/10.1007/s40820-020-00469-3

Nano-Micro Lett. (2020) 12:131 Page 3 of 29 131
of water splitting [22–24]. If the generated gas bubbles are both anode and cathode in two-electrode system; the whole
difficult to break away from the surface of electrode, the voltage for electrochemical water splitting was 1.68 V to
active site of electrocatalyst will be covered as well as the achieve 20 mA cm−2 in 1.0 M KOH (Fig. 2b) [53]. He and
electrolyte will be difficult to diffuse to access the interface Sun et al. synthesized a bifunctional catalyst for electrolysis
of catalyst/electrolyte [25]. Therefore, the hydrophilicity and of water based on three-dimensional (3D) self-supported Fe-
aerophobicity of the electrode is very significant to promote doped Ni2P nanosheets on NF. An two-electrode electrolyzer
the efficiency and stability of the water splitting process [26, composed of the (Ni0.33Fe0.67)2P||(Ni0.33Fe0.67)2P electrodes
27]. Hence, the development of a high active, stable and required a low cell voltage of 1.49 V to achieve 10 mA cm−2
low-cost bifunctional electrocatalyst for water splitting is in 1.0 M KOH [45]. Wang et al. reported that the nanostruc-
imperative [28]. tured porous N i3FeN nanosheet was obtained by annealing
process the Ni3Fe LDHs precursor in NH3 atmosphere. The
2.1 Electrocatalysts for Overall Water Splitting porous Ni3FeN used as both anode and cathode in two-
electrode system for overall water splitting in 1.0 M KOH
For overall water splitting, an ideal bifunctional electro- required a voltage of 1.495 V at 10 mA cm−2, which could be
catalyst should be a low-cost, highly active and economical driven by a battery with rated voltage of 1.5 V [50]. Metal-
preparation method, which can provide long-term stability free electrocatalysts also show high activity, good stability
for both HER and oxygen evolution reaction (OER) in the and low cost to replace metal-based electrocatalysts for long-
electrolyte [29]. The employment of suitable catalyst will term water splitting [54, 55]. Yu, Chen, Dai et al. reported
be critical to develop electrolysis of water. Hence, it is an a novel metal-free bifunctional electrocatalyst with the
urgent desire for researchers to develop many different kinds ultrathin exfoliated black phosphorus (EBP) nanosheets on
of bifunctional electrocatalysts with different performance N-doped graphene (EBP@NG). EBP@NG possessed excel-
to promote the development of H2 fuels [30]. lent performance of HER and OER in 1.0 M KOH. The volt-
Transition metal oxide [31, 32], transition metal sulfides age of an optimized two-electrode cell with EBP@NG used
[33–39] and selenides [40–43], transition metal phosphides as anode and cathode was 1.54 V to achieve 10 mA cm−2
[44–49], transition metal nitrides [50–52] become poten- [54]. The voltage of most reported bifunctional non-noble
tial candidates as non-noble metal electrocatalysts for elec- metal electrocatalysts is lower than that of benchmarking
trolysis of water. The Ni3S2/MnS–O nanosheets on Ni foam IrO2||Pt electrodes (1.57 V at 10 mA cm−2) and standard
(NF/T(Ni3S2/MnS–O)) were employed as anode and cathode coupled Ni and stainless steel (1.73 V at 10 mA cm−2) in
for overall water splitting (Fig. 2a), which was required a the industrial application [56]. A detailed comparison of the
voltage of 1.54 V at a current density of 10 mA cm−2 [33]. HER and OER activities of recently reported electrocatalysts
Dai and Liu et al. prepared NiCo-nitrides/NiCo2O4/GF as for overall water splitting are listed in Table 1.
(a) (b)
− +
HER e− e− OER
HER OER
H2 O2
O2
H2 HER OER
Fig.  2 a Schematic diagram of two-electrode configuration for overall water splitting with NF/T(Ni3S2/MnS–O) as anode and cathode. Repro-
duced with permission from Ref. [33]. Copyright 2019 Elsevier Inc., b photographs showing the NiCo-nitrides/NiCo2O4/GF||NiCo-nitrides/
NiCo2O4/GF couple electrolyzer. Reproduced with permission from Ref. [53]. Copyright 2019 John Wiley and Sons
13
Table 1 Summary of the HER and OER activities of recently reported electrocatalysts for overall water splitting
Catalysis Electrolytes ƞ for HER ƞ for OER Tafel slope Tafel slope Overall volt- References
at j (mV@ at j (mV@ for HER (mV for OER (mV age at j (V@
mA cm−2) mA cm−2) dec−1) dec−1) mA cm−2)
Co3O4@C@NF 1.0 M KOH 42@10 96@10 56 89 1.40@10 Ha et al. [31]

NF/H–CoMoO4 1.0 M KOH 295@10 – 91 – 1.56@10 Chi et al. [32]
NF/T(Ni3S2/MnS–O) 1.0 M KOH 116@10 228@10 41 46 1.54@10 Zhang et al. [33]
N–CoS2/NF 1.0 M KOH 28@10 200@20 42.6 55 1.50@10 Yao et al. [34]
MoS2/NiS 1.0 M KOH 244@10 370@11 97 108 1.64@10 Qin et al. [35]
MoS2–Ni3S2 HNRs/ 1.0 M KOH 98@10 314@10 61 57 1.50@10 Yang et al. [36]
NF
Ni3S2/NF 1.0 M KOH 189@10 296@10 89.3 65.1 1.55@10 Li et al. [37]
MoS2/NiS2 1.0 M KOH 62@10 278@10 50.1 91.7 1.59@10 Lin et al. [38]
Ni3Se4@NiFe LDH/ 1.0 M KOH 85@10 223@10 98.6 55.5 1.54@10 Zhang et al. [40]
CFC
CoSe@NiFe LDH/ 1.0 M KOH 98@10 201@10 89 39 1.53@10 Sun et al. [41]
NF
Co–Ni–Se/C/NF 1.0 M KOH 90@10 275@30 81 63 1.6@10 Ming et al. [42]
MoSe2/MXene 1.0 M KOH 95@10 340@10 91 90 1.64@10 Li et al. [43]
CoP2/RGO 1.0 M KOH 88@10 300@10 50 96 1.56@10 Wang et al. [44]
(Ni0.33Fe0.67)2P 1.0 M KOH 214@50 230@50 – 55.9 1.49@10 Li et al. [45]
NF@Fe2–Ni2P/C 1.0 M KOH 39@10 205@10 30 52 1.57@100 Sun et al. [46]
NiCoP@NC NA/NF 1.0 M KOH 37@10 305@50 53.9 70.5 1.56@20 Cao et al [47]
CoFeP TPAs/Ni 1.0 M KOH 43@10 198@10 65.3 42 1.47@10 Zhang et al. [48]
Mo–NiCoP 1.0 M KOH 76@10 269@10 60 76.7 1.61@10 Lin et al. [49]
Ni3FeN 1.0 M KOH 45@10 223@10 75 40 1.495@10 Wang et al. [50]
Ni3N–NiMoN 1.0 M KOH 31@10 277@10 64 118 1.54@10 Wu et al. [51]
CoAl–Fe2N/Fe3N 1.0 M KOH 145@10 307@10 54 69 1.67@10 Hu et al. [52]
NiCo-nitrides/ 1.0 M KOH 71@10 183@10 41 54 1.68@20 Liu et al. [53]
NiCo2O4
EBP@NG 1.0 M KOH 125@10 265@10 76 89 1.54@10 Yuan et al. [54]
2.2 Electrolytic Cell [59–64]. In the AWE, the electrolyte is made up of a caustic

potassium solution with a concentration of 20–30% KOH
Conventional water electrolysis usually utilizes transition [65–67]. The configurations of alkaline electrolyzer con-
metal catalysts and diaphragms in alkaline electrolytes (alka- tain the conventional alkaline electrolyzer, the “zero-gap”
line water electrolysis, AWE) or noble metal catalysts and alkaline electrolyzer and the membraneless or decoupled
a proton exchange membrane in acidic media (PEM water alkaline electrolyzer.
electrolysis) [57, 58]. In conventional alkaline electrolyzer, the anode and cath-
ode immersed in the electrolyte are located on either side
of the flat current collector to facilitate a serial connection
2.2.1 Alkaline Water Electrolysis between cells [68]. H2 and O2 bubbles are formed in two
electrolyte chambers; meanwhile, a membrane avoids the
Since Troostwijk and Diemann first found the phenomenon mixture of them (Fig. 3a). This method is easy to scale up to
of electrolysis of water in 1789, alkaline water electroly- the massive volume production of H 2. However, the result-
sis has been an established technique for H 2 production. ing bubbles decrease the effective area of the electrodes
Therefore, alkaline electrocatalysis is the most widely used and improve the resistance of the electrolytes, leading to
electrolysis technology on a business level in the world low current densities. Another issue of AWE of Ni-based

positively charged
(a) H2 O2 (b) (1) particle (2) (3) (4)
forced
− + convection
negatively polarized cathode
formation of
single particle
“insoluble”
collision
particle agglomerate
(c)
I II III
inactive impurity catalyst particle

Voltage
separator electrodes electrolyte
Time
Fig.  3 a Schematic diagram of conventional alkaline electrolyzer. Reproduced with permission from Ref. [68]. Copyright 2012 Elsevier Inc.,
b schematic diagram of the formation of the catalyst film, c schematic diagram of cathode deactivation caused by the deposition of trace metal
impurities and the change of the overall voltage in the electrolytic cell. Reproduced with permission from Ref. [69]. Copyright 2018 Elsevier Inc
electrodes is the sustaining attenuation of the activity for a zero-gap cell configuration could reduce 30% in ohmic
HER and OER. The deposition of metal cations mainly from resistance in comparison with the traditional a 2-mm gap
electrolyte impurities can generate a surface coating with in alkaline electrolyte (Fig. 4a, b). At all current densities,
low catalytic activity, leading to reducing the activity for especially over 500 mA cm−2, the performance of zero-gap
HER. Therefore, Schuhmann and Ventosa et al. creatively configuration cell was better than the standard cell. In addi-
brought forward a method based on in situ self-assembly tion, the foam electrodes with high surface area allowed for
of catalyst particles in the electrolytic process to obtain a low ohmic resistance compared to the coarse mesh elec-
exceptionally stable catalytic films with the capability of trodes. Therefore, the zero-gap configuration will permit
self-healing (Fig. 3b, c). They showed that the passivation low cost and high-efficiency alkaline electrolysis [70]. The
of cathode by zinc impurities from the electrolyte could be anode and cathode also can be fabricated on the separators
surmounted by immobilizing catalyst with self-assembly and to further decrease the distance of the gap [71]. For instance,
self-healing films. In the electrolytic process, zinc impurities Tour et al. used the laser-induced graphene (LIG) to form
deposited on the cathode electrode in the form of a dendritic HER and OER catalysts on each side of a polyimide (PI)
film increased the HER overpotential, but the continued self- film to assemble high-efficiency electrodes for electrolysis
assembling and self-healing of the catalyst films following of water. In this alkaline electrolyzer, LIG was patterned on
obscured the zinc dendrites that restored the favorable over- each side of a PI film and subsequently assembled LIG-Co–P
potential of the HER [69]. and LIG-NiFe on opposite sides by electrochemical deposi-
In the “zero-gap” configuration, a thin cellulose felt tion (Fig. 4c, d). The hydroxide ions could migrate through
occupied the intra-electrode space can absorb the electro- a small pinhole at the end of the film that may be covered
lyte, which is confined and clamped between two hydro- by ion exchange membranes for large-scale applications. As
philic separators that are tightly pressed on the anode and expected, the device of LIG-Co–P and LIG-NiFe for water
cathode. The anode and cathode ought to be polyporous to splitting required 1.66 V to achieve a current density of
permeate the liquid electrolyte. Therefore, the bubbles from 10 mA cm−2 in 1.0 M KOH [72].
the inner space of the electrode can be efficiently excluded In alkaline water electrolysis, the conductivity of liquid
[68]. For instance, Dunnill et al. reported that employing electrolyte is much higher than that of the ion exchange
13
(a) Zero Gap Cell (b)

Porous electrodes
Electrolyte
Gas out
− +
Electrolyte In
Interelactrode Gap
Gas Separator
(c) (d) For HER For OER
e−
Device
H 2O OH−
H2 O2
LIG-Co-P LIG-NiFe
Clip
pinhole
Fig.  4 a Schematic diagram for reducing the gap between electrodes by using a zero-gap cell, b components for the zero-gap cell, including the
machined flow field plates, silicone gaskets, mesh electrodes and Zirfon gas separator. Reproduced with permission from Ref. [70]. Copyright
2017 Elsevier Inc., c schematic diagram and d a photograph of an integrated LIG electrolyzer. Reproduced with permission from Ref. [72].
Copyright 2017 American Chemical Society
membrane leading to significant ohmic losses [73, 74]. To further promote the purities of the produced gas in
Therefore, Gillespie and Kriek constructed a membraneless the DEFT electrolyzer, Gillespie and Kriek developed an
DEFT alkaline electrolyzer for the gainful production of H 2. extensible and simple mono-circular filter press (MCFP)
The electrolyzer could overcome the limitation of current reactor for the DEFT alkaline electrolysis (Fig. 5d). Under
density threshold in the existing technology and was an ideal the condition of the flow rate (0.075 m s−1) and electrode
choice for H2 generation (Fig. 5a). The scale-up of the tech- gap (2.5 mm), the utilized gas/liquid separation methodol-
nology represented a difference from the design of original ogy improves the gas purities of H
2 to 99.81 vol% and O
2 to
tested stack, which encapsulated many slender electrodes 99.50 vol%. Each round mesh electrode pair of 30 mm has
in a pressure filter assembly (Fig. 5b, c). The operation independent pressurized chamber and indirect injection of
parameters of the pilot plant were limited to low flow rate, the electrolyte. By incorporating a gas purge, the high gas
and the electrode gap was 2.5 mm. The performance of the purity could be kept for a long running time. Using a Ni/Ni
pilot plant is consistent with the previous acquired results. catalyst, the current density was 1.14 A cm−2 (2.5 VDC)
The geometric area of mesh electrodes used for the perfor- at a flow rate of 0.075 m s−1, 60 °C and 2.5-mm electrode
mance test of plant was 344.32 cm2. Under the conditions of gap. Under the same condition except the utilization of a
0.04 m s−1, 30% KOH, 2 V direct current (VDC) and 80 °C, double-layer mesh electrode, a current density reached to
the best performance of the NiO anode and Ni cathode com- 1.91 A cm−2 at 2.5 VDC was realized, confirming that the
bination reached to 508 mA cm−2. Unfortunately, due to the multilayer microporous electrodes for the DEFT principle
nature of the gas–liquid separation system, the gas mass was were available [76].
insufficient in comparison with previous results [75].

(a) (b) (d) PURGE GAS OUTLET
PAIR 1 PAIR 2 PAIR n
BI-PHASE
COLLECTION
CHAMBERS
H2 O2
(c)
H2 H2 (e) ELECTROLYTE PRESSURE CHAMBERS
O2 O2
O2 H2*R
H2 H2 Muti-cell system
O2 O2
LEGEND: H2 H2
Water
ELECTROL YSER SHELL inlet
Cell
CONDUCTOR PLATES Cell
Cell
B
C-Z
A
ANODIC ELECTRODE
CATHODIC ELECTRODE
ELECTROLYTE Solution
OXYGEN BUBBLES
HYDROGEN BUBBLES
Fig.  5 a Schematic diagram of filtration mesh electrode encapsulated in a single injection assembly, b a photograph of the horizontal filter press
DEFT electrolyzer stack, and c a diagram of a cross section of the electrolyzer stack assembly. Reproduced with permission from Ref. [75].
Copyright 2017 Elsevier Inc., d cross section of the DEFT electrolyzer stack in a MCFP configuration. Reproduced with permission from Ref.
[76]. Copyright 2018 Elsevier Inc., e schematic diagram of the multicell system by the E-TAC process. Reproduced with permission from Ref.
[83]. Copyright 2019 Springer Nature
Utilizing decoupled the two half-reactions of water split- 2.2.2 PEM Water Electrolysis
ting by redox mediators can completely avoid the mixture of
produced H2 and O2, which is promising for large-scale prac- In 1960s, General Electric firstly proposed a concept of
tical application [77–82]. Grader et al. proposed a two-step solid polymer electrolyte (SPE) concept for water elec-
electrochemical-thermally activated chemical (E-TAC) cycle trolyzer, which predicted to conquer the disadvantages of
for overall water splitting. H2 was produced by a HER at the alkaline electrolyzers. Grubb idealized the above concept
cathode. The traditional OER was replaced by two steps. In by using solid sulfonated polystyrene membranes as the
the first step, the Ni(OH)2 anode was oxidized to NiOOH electrolytes, also known as PEM water electrolysis, rarely
by four one-electron oxidation reactions. In the second step, called SPE water electrolysis [84, 85]. The polymer elec-
the oxidized NiOOH could be spontaneously reduced to trolyte membrane could provide higher proton conductiv-
Ni(OH)2 in an exergonic chemical reaction to simultane- ity, lower gas exchange, the compact design of system and
ously achieve O2 production and anode regeneration. As operate under high pressure [86–90]. The advantages of
shown in Fig. 5e, they also assumed a multicell system with solid polymer electrolyte were lower membrane thickness
fixed anodes and cathodes in each cell for practical appli- (~ 20–300 μm thick).
cation to produce pure H 2 and O 2 gas. A low-temperature First of all, the catalyst layer was coated on a glossy
electrolyte flew through cell A, driving the produced H2 to polytetrafluoroethylene (PTFE) sheet; then, the coating
the H2 separator. Meanwhile, a high-temperature electrolyte consisted of catalyst and Nafion ionomer on the surface
flew through cell B to regenerate the anode, driving the gen- of a Nafion 117 membrane was flat when the PTFE sheet
erated O2 to the O2 separator. In this multicell system, only was removed after being pressed against the membrane.
hot and cold electrolyte moved in the operation process [83]. The edge between the catalyst coating and membrane was
13
(a) PEM electrolysis (b) PEM electrolysis Catalyst coated membrane

20-100 °C Overview of components
Catalyst coating
Cathode − + Anode
Membrance
H2 H+ 1/2 O2 100 µm
PEM electrolysis R&D

500 µm
H2O · Reduction or substitution
Current collector of noble catalysts
· Reduce costs of current
Cathode Anode collectors and separator
Pt Ir plates
· Develop micro porous layer
Membrane
· Improve membrane
characteristics
H2O → 2H+ + 1/2O2 + 2e− Anode
· Enhance long-term durability
2H+ + 2e− → H2 Cathode
H2O → H2 + 1/2O2 Totalreaction · Develop stack concepts (MW)
Separator plate
Fig.  6 a Schematic diagram of the working principle and b composition of a PEM water electrolysis. Reproduced with permission from Ref.
[65]. Copyright 2013 Elsevier Inc
obvious on the surface of membrane. The thickness of the crossover rate of the polymer electrolyte membrane allowed
coating could change by adjusting the amount of catalyst for the PEM electrolyzer to operate at a wide range of power
ink [91]. In commercial PEM water electrolyzer, a layer input.
consisted of Pt/C and Nafion ionomer, similarly a layer of The phenomenon of cross-permeation enlarged along
made up of IrO2 or RuO2 catalyst and Nafion ionomer, was with high operational pressure in PEM electrolysis [92].
coated on the opposite side of a Nafion 117 membrane, High pressures (over 100 bar) required thicker membranes
respectively (Fig. 6a). to reduce the mixture of H
2 and O
2, which kept the marginal
The anode side of the PEM water electrolyzer was filled concentrations below the safety threshold (4 vol% H2 in O2)
with water. Water successively passed through the sep- [92]. The corrosive acidic regime in the PEM electrolysis
arator plates and current collectors. When water got to required distinct materials, which needed the resistance to
the surface of catalyst layer, the molecules of water were severe corrosive low pH corrosion (pH ~ 2) and kept at high
broken up into protons, electrons and diatomic oxygen. overvoltage (~ 2 V).
Subsequently, the generated protons left the anode through
the ionomer and the membrane, passing through the side 2.2.3 Seawater Electrolysis
of the cathode, where they coupled with electrons to form
H2 after they arrived the catalytic layer. Then the H2 must Water electrolysis systems usually consist of two half-reac-
flow through the cathode collector and the barrier, away tions: HER at the cathode and OER at the anode. Compared
from the cell. At the same time, the electrons left the cath- to the limited pure water, seawater is the most abundant
ode catalytic layer via the current collector, the separator aqueous electrolyte on earth for the utilization in the process
plates, then departured to the side of the cathode. O2 must of water electrolysis. Seawater electrolysis was investigated
flow back via the catalyst layer and current collector to by Bennett [93], which was composed of HER at the cathode
the separator plates then go out of the cell (Fig. 6b) [65]. and chlorine evolution reaction (ClER) at the anode [66].
The PEM electrolyzers could work at high current densi- ClER is a two-electron process, and chlorine or hypochlorite
ties of over 2 A cm−2, reducing the operating cost and the is the value-added product [94]. Four years later, Trasatti
potential total cost of water electrolysis. The ohmic losses
used different anodes for seawater electrolysis to investigate
confined the maximum value of current densities. The thin
the selectivity for anodic process [95]. In 2016, Dionigi et al.
membrane capable of providing good proton conductivity
proposed the chemical limitations of seawater electrodes and
and high current densities could be achieved. The low gas

3.5
(a) CE (Pt) WE(RuO2/Ti) RE (b) 100
3.0
Faradaic efficiency (%)

80
Cell voltage (V)

2.5
60
2.0
40
+2e− 1.5
−2e−
H+
NaCl NaCl 20 1.0
Cathodic part Anodic part 0 0.5

1.30 1.35 1.40 1.45 1.50
H+ H2 Cl− ClO− OH− Potential (V vs. RHE)
Fig.  7 a Schematic of the electrocatalytic cell for cathodic HER and anodic hypochlorite production, b dependence of the FE of hypochlorite
with the applied potentials on the cathode and the cell voltage. Reproduced with permission from Ref. [97]. Copyright 2019 Royal Society of
Chemistry
presented the design criterion for selective seawater splitting way is using a tandem structure to generate a total photo-
catalysts [96]. voltage through complementary light absorption between
In the seawater electrolysis system, the membrane (such different semiconductor electrodes [103–113].
as Zirfon) should be physically robust and insusceptible Mathews et al. constructed that a Fe2O3 photoanode in
to blockages, because largely block either anions or cati- tandem with an organic–inorganic CH3NH3PbI3 perovskite
ons (such as H +, Na+, OH− and Cl− and so on) are able solar cell (PSC) (Fig. 8a) could achieve overall unassisted
to migrate through the membrane [66]. A commercial water splitting at air mass 1.5 global (AM 1.5G) irradia-
ruthenium oxide-coated titanium electrode (RuO2/Ti) and tion with a solar-to-hydrogen (STH) conversion efficiency
Pt electrode were served as the working electrode and the of 2.4%. The total potential produced by this tandem sys-
counter electrode, respectively, to achieve ClER at the anode tem reached to 1.87 V, which was surpassed the required
and HER at the cathode (Fig. 7a). The FE of hypochlorite thermodynamic and kinetic potential of 1.6 V, deliver-
increased linearly with the applied potential on the anode, ing water splitting with no external energy consumption
which could achieve 99% at the applied potential of 1.5 V [114]. Jun and Lee et al. reported that cobalt carbonate-
vs. RHE on the RuO2/Ti electrode (Fig. 7b) [97]. catalyzed, H and 3 at% Mo dual-doped BiVO4 (Co–Ci/H,
3% Mo:BiVO4) device in series with C H3NH3PbI3 single-
3 Water Splitting Driven by a Photoelectrode junction PSC could realize wireless solar water splitting
under AM 1.5G without external energy supply (Fig. 8b).
Device
The STH efficiency of the device exhibited STH effi-
Electrolyzed water can effectively generate H 2 through a ciency was 3.0%, which could be even higher along with
two-electrode system. However, it takes a large amount of the improvement of the photoanode performance [115].
electrical energy to conquer the thermodynamic barrier Luo et al. reported that a semilucent CH3NH3PbBr3 PSC
as the top absorber pairing with a C uInxGa1−xSe2 (CIGS)
in the electrolysis of water. In the photoelectrochemical
multilayer photocathode as the bottom absorber could
(PEC) electrolysis cell [98, 99], the photoanode absorbs
panchromatic harvest of the solar spectrum for effective
the solar energy to generate the photovoltage to effectively
overall water splitting (Fig. 8c). For this PV-PEC system
drive water splitting, which can effectively decrease the
employing a single-junction PSC as the bias source at AM
external energy consumption [100–102]. To minimized
1.5G irradiation, a STH efficiency was reached to over 6%.
utilization of the external energy consumption and realize
Moreover, the efficiency could attain over 20% by further
unassisted overall light-induced water splitting, a possible
13
(a) Hematite (b) (c) e−

h+
O2
Au Co-Ci/H, 3% Mo:BiVO4
H2
Spiro
O2 H2
Perovskite
FTO/glass
Pt
Cu
TiO2
TiO2 blocking
layer Pt
FTO
TiO2/CH3NH3PbI3/PTAA/Au DSA CIGS Perovskite

Glass
(d) (e) Bipolar FTO Substrates
− O2 bubble
H2 bubble
(f)
Ag Ti(Nb)Ox
+ PCBM
MAPbI3
FTO
NiMgLiO
PSC Glass
> 515 nm 2H2O + 2e−
Quartz cell Electrolyte
DSSC
S2− + SO32− + 2h+
1 sun
Pt
< 515 nm Mo:BiVO4 S2O32− H2 + 2OH−
High VOC Pt coated FTO
BiVO4/WO3 (as the counter Pt mesh
Beam splitter Nafion DSSC Na2S
embedded of tandem device) QD-Dye Tandem
structure Pt counter Na2SO3
of DSSC Dye absorbed TiO2
Fig.  8 a Schematic of the dual-junction PSC/hematite photoanode tandem cell. Reproduced with permission from Ref. [114]. Copyright 2015
American Chemical Society, b configuration consisted of Co–Ci/H, 3% Mo:BiVO4 and T iO2/CH3NH3PbI3 tandem cell. Reproduced with per-
mission from Ref. [115]. Copyright 2015 American Chemical Society, c schematic of the perovskite and CIGS tandem water splitting cell.
Reproduced with permission from Ref. [116]. Copyright 2015 John Wiley and Sons, d the configuration of the PEC-PSC tandem device. Repro-
duced with permission from Ref. [117]. Copyright 2016 American Association for the Advancement of Science, e schematic of the WO3/BiVO4
photoanode tandem configuration. Reproduced with permission from Ref. [120]. Copyright 2015 Elsevier Inc., f scheme of the PEC-DSSC tan-
dem cell. Reproduced with permission from Ref. [121]. Copyright 2013 American Chemical Society
optimizing the performance of the perovskite top absorber PEC tandem cells was retained 80% after more than 8 h,
[116]. Qiu et al. constructed a single PSC in tandem with which attributed to the degradation of DSSC. Therefore, the
nanoporous Mo-doped B iVO 4 (Mo:BiVO 4 ) photoan- layout relied on chosen redox mediators and catalysts for the
ode PEC cell device by using a beam splitter to divide a DSSC and photoanodes, respectively [119]. Wang and Park
standard sunlight beam into two light beams (Fig. 8d). The et al. demonstrated a 5.7% STH without any external bias
PSC-PEC serial system achieved unassisted water splitting unassisted monolithic tandem system, which was combined
with a STH efficiency of 6.2% and long-term stability over the high transparency of B
iVO4-sensitized mesoporous WO3
10 h (only 5.8% decay) [117]. films/Pt with a single DSSC (Fig. 8e). On one hand, the
Owing to the energy supply is efficient and the materi- BiVO4 coating on the porous WO3 films maintained the high
als (e.g., T
iO2) are cheap, abundant and environmentally transparency, allowing enough photons to enter the dye-sen-
friendly, dye-sensitized solar cell (DSSC) in tandem with sitized photoanode. On the other hand, the porphyrin-dye-
photoelectrodes are prospective system for unassisted water sensitized photoanode with a cobalt electrolyte produced
splitting [118]. Herein, Sivula et al. constructed a device enough potential to achieve wireless solar water splitting
based on an oxide (WO3 or Fe2O3) photoanode in series in the tandem system [120]. Mora-Sero and Gimenez et al.
with a DSSC for unassisted water splitting. In this device, established a tandem device combined a CdS quantum dots
the light was incident on the photoanode before the under- modified TiO2 photoanode connected with a DSSC for
lying DSSC. The WO3/DSSC serial system reached a STH water splitting with no external bias (Fig. 8f). This device
conversion efficiency of 3.10%, while that of 1.17% in the showed a STH conversion efficiency of around 0.78% and
Fe2O3/DSSC tandem device. For the two tandem cells, the high stability. Designing hybrid photoanodes with different
optical transmittances and spectral responses matched with light absorbers was important for developing efficient water
the bandgaps of oxide, determining the photocurrent and splitting devices [121].
performance of devices. The performance of F e2O3/DSSC

4 Water Splitting Driven by Solar Cells of 10 mA cm−2, corresponding to a STH conversion effi-
ciency of ~ 9.2% [127]. Shen et al. also reported that three
As energy storage systems, solar cells, including Si solar Si solar cells in series (entire area of 3 cm2) were combined
cells, CIGS solar cells, PSCs, organic solar cells (OSCs) and with the double-layer Ni–Co–S/Ni–Co–P electrocatalyst on
DSSCs [104, 122–124], are able to transform surplus solar NF (NCS/NCP/NF) electrodes for unassisted water splitting
energy into storable and distributable energy carriers. The (Fig. 9b). When using NCS/NCP/NF as a bifunctional cata-
photovoltage of series connected solar cells can drive water lyst for water splitting, the current density of 10 mA cm−2
electrolysis [125]. can be obtained with only 1.49 V. Finally, the whole solar
water splitting was realized with the efficiency of STH
reached to 10.8% [122]. Oh, Ryu and Kim et al. combined
4.1 By Conventional Solar Cells
four Si heterojunction solar cells in series with a bifunc-
tional NiFe nanostructures electrocatalyst to realize water
For photovoltaic (PV)-driven water splitting, several con-
splitting (Fig. 9c). The overpotential of NiFe inverse opal
nected crystalline conventional solar cells (such as Si and
electrolyzer for water splitting was ~ 160 mV, achieving a
CIGS solar cells) are prospective because of the high STH
STH conversion efficiency of 9.54% more than 24 h with no
efficiency and solar-driven durability for H
2 production [60,
bias condition [128].
104, 126].
Compared to Si solar cell, the outstanding advantage
Gan and Zhang et al. proposed a bimetallic compound
of CIGS is that the band gap energy can be modulated to
NiFeSP on the commercial NF (NiFeSP/NF) in series with
effectively absorb the solar spectrum, so it is also widely
a Si solar cell to implement overall water splitting (Fig. 9a).
used to achieve water splitting [129–131]. For purpose of
The voltage of combination of the Si solar cell and the
overcoming the problem of low energy to drive overall water
bifunctional NiFeSP/NF electrodes for water splitting in
splitting, connected series into a monolithic device can be
the tandem system was 1.58 V to reach a current density
(a) Cell voltage/V (b) (c)
− + OER HER
− − +
NF
+
NFO2 OER HER

H2
NiFeSP
(d) photocurrent (e) photocurrent

Potentiostat
O2 H2
hν 2H2O O2
Ag/AgCl
e− h+ H2
hν 2H2O
4H+ + O2 e−
hν h+
e− h+ 2H2O
H2 + 2OH−
e− h+
2H2O
hν e−
4H+ + O2
e− h+ h+
H2 + 2OH−
Cu/Ag/ZnO:Al/ZnO/CdS/ClGS/Mo/glass
Fig.  9 a Schematic diagram of the solar-driven system with a Si solar cell for overall water splitting. Reproduced with permission from Ref.
[127]. Copyright 2017 American Chemical Society, b unassisted water splitting using NCS/NCP/NF as the electrodes and Si solar cells as the
light absorber. Reproduced with permission from Ref. [122]. Copyright 2018 Royal Society of Chemistry, c unassisted water splitting by using a
combination of an NiFe electrolyzer and Si solar cells. Reproduced with permission from Ref. [128]. Copyright 2017 Elsevier Inc., d schematic
diagram of the CIGS absorber connected with the catalyst module by wires. Reproduced with permission from Ref. [132]. Copyright 2013 Royal
Society of Chemistry, e schematic diagram of the CIGS electrode connected with a working electrode with deposited catalyst in the electrolyte
by wires. Reproduced with permission from Ref. [133]. Copyright 2013 Elsevier Inc
13
adopted to supply enough to drive the whole reaction. For efficient absorbent material for water cracking was dem-
example, Jacobsson et al. reported that three series-inter- onstrated. They confirmed the full potential of CIGS as a
connected compound semiconductor CIGS PV electrolysis highly effective absorbent material could be used for water
could efficiently realize solar water splitting at AM 1.5G splitting [133].
irradiation (Fig. 9d). The current density was centered at
8.5 mA cm−2 and a STH conversion efficiency reached to
4.2 By Perovskite Solar Cells
10.5% [132]. Jacobsson et al. demonstrated CIGS solar cell
could be applied to water splitting into H
2. They used a p–n
In the above tandem system for water splitting in Sect. 4.1,
junction for separating the charge and a catalyst deposited
owing to the low open-circuit voltages of Si solar cells, at
on the surface to significantly improve the performance in
least three to four connected cells in series must be utilized
the configuration of a PEC cell (Fig. 9e). In this device,
to achieve reasonable efficiency. In contrast, PSCs have
the efficient charge separation production from the cataly-
achieved open-circuit voltages at 0.9 V and up to 1.5 V
sis improved the durability of CIGS in the light irradiation.
[134–139], which is sufficient for efficient water splitting
Furthermore, photocurrents in this device could reach to
by connecting just two in series [123]. Grätzel reported
over 20 mA cm−2. The full potential of CIGS as a highly
that the tandem PSC could be used to drive electrolytic
(a) (b)
sp
iro H 3N TiO 2
-M H 3
C O/
eO Pb
FT
TA I 3
+ −
Ni
D/
Fe
Au
-L
DH
(−) e−
ηHER
0 H2O/H2
1.5 eV
e−
VRHE
O2
H2
O
OH− H2 h+
+1.23 O2/OH−
ηOER
H2O
(+)
Ni
h+
Fe
-L
DH
(d)
(c) All-inorganic
− + perovskite solar cells
NF-8-A/CFP
NF-8/CFP
O2 H2
H2 O2
H2O OH−
Per
ov
Sol skite OH− H2O
ar c
ell
Duckweed Electrolyzer
Fig.  10 a Schematic diagram and b a generalized energy of the tandem PSC for water splitting. Reproduced with permission from Ref. [140].
Copyright 2014 American Association for the Advancement of Science, c schematic diagram of the solar energy-driven overall water splitting
device with a PSC. Reproduced with permission from Ref. [141]. Copyright 2018 Royal Society of Chemistry, d configuration of the electro-
lyzer with the Ni0.5Co0.5P/CP bifunctional electrocatalyst and all-inorganic PSCs under irradiation. Reproduced with permission from Ref. [123].
Copyright 2018 Royal Society of Chemistry

splitting of water. The configuration was a water splitting that the surface of commercial TE device is unserviceable to
system combing with a solution-processed tandem PSC and absorb the infrared light. In order to improve the efficiency
NiFe LDH used as anode and cathode electrodes in alka- of TE devices, it is necessary to expand the absorption of
line electrolyte (Fig. 10a, b). A photocurrent density of the infrared light by TE devices [151]. This requirement enlight-
tandem two-electrode system was around 10 mA cm−2, cor- ened us to develop the probability of integrating photother-
responding to a STH efficiency of 12.3% [140]. Bhattachar- mal materials on the TE device to promote the efficiency of
yya et al. developed NiFe-alloy nanoparticles supported by photo-thermoelectric conversion [153]. Generally, materials
N, S-doped mesoporous carbon matrix from duckweed as with higher photothermal conversion efficiency include the
efficient electrocatalysts (Fig. 10c). For overall water split- Group VIII metal materials, graphene oxide (GO) [154],
ting, only 1.61 V was required to attain a current density of carbon nanomaterials, transition metal oxides (e.g., M oO2,
10 mA cm−2 for over 200 h. Combining with PSCs, the elec- WO3, Fe2O3) and chalcogenides (e.g., Cu2S) [155]. In 2014,
trolyzer for overall water splitting showed a STH efficiency the photothermal effect of GO had been demonstrated for the
of 9.7%, which is completely powered by solar energy [141]. first time for TE devices [153]. The GO drop-coated on the
Jin et al. reported that bifunctional bimetallic phosphide surface of the TE device could transform the infrared light
(Ni0.5Co0.5P/CP) in tandem with all-inorganic PSCs (based to the electricity, which was directly utilized to carry out
on a CsPb0.9Sn0.1IBr2 light absorber and a nanocarbon elec- photoelectrocatalytic process in the case of no applied volt-
trode Fig. 10d) realized efficient overall water splitting. The age. As could be seen from the infrared thermal image, the
water splitting electrolyzer could achieve a current density conclusion that the surface coating of GO could significantly
of 10 mA cm−2 at only 1.61 V. Driven by stabilized all- increase the response of TE devices can be drawn. Our group
inorganic PSCs, the electrolyzer delivered a STH conversion employed carbon nanoparticles (CNP) light absorbent layer
efficiency of 3.12% and good durability [123]. on the top to increase the absorption efficiency of STEGs. A
very easy candle flame preparation method was employed to
synthesize the black CNP layer on the hot end of the com-
5 Water Splitting Driven by Thermoelectric
mercial TE device (CNP generator). The synthesized CNP
Device
layer had a 3D porous structure which was conducive to
capture light, and the power produced by this STEG device
Water splitting driven by solar cell is a common energy-
could drive an electrolyzer for splitting water to produce
driven water splitting strategy. However, the utilization effi-
H2 (Fig. 11a, b). In this water splitting system driven by
ciency of sunlight by the solar cell is relatively low because
TE device, 6 sets of CNP coated thermoelectric generator
solar cells are chiefly effective in the range of ultraviolet
devices were series connection to supply adequate voltage
and visible light. Conventional semiconductor solar energy
for electrolysis of water. After connecting the TE generator
conversion technology cannot efficiently utilize the infrared
with the electrochemical cell, the cathode and anode imme-
light, which occupies nearly half of the sunlight. The com-
diately generated plenty of bubbles under the sunlight irra-
bination of TE device and infrared-active materials supplies
diation. The production of H 2 and O
2 was at an average rate
a particular approach to transform infrared sunlight to the
of 20 and 10 μmol h−1, respectively, and the rate at the time
electricity, which improves the solar energy utilization effi-
between 11:40 and 12:40 was highest on account of the max-
ciency [142–147]. Thus, the study of water splitting driven
imum sunlight intensity (Fig. 11c). This study demonstrated
by TE device is extensively performed.
that the output voltage of TE device was able to drive the
H2 production from water splitting by coating nanomaterials
5.1 By Surface‑Modified Thermoelectric Device with photoabsorbing and photo-to-heat conversion proper-
ties on the hot end of TE devices [156]. Inspired by the dual
The infrared light usually delivers the energy in the form of model effects of surface plasmon resonance (SPR) photo-
heat through photothermal effect [148, 149]. Transforming thermal conversion and efficient electrocatalytic activity for
the released heat into available energy (e.g., electricity) is a group VIII metals, our group then proposed Ni nanosheets
distinct method to utilize the infrared light. This conversion array grown on the surface of TE device for electroly-
can be probable realized by TE device [150–152]. It is a pity sis of water. In the integrated device, Ni nanosheets array
13
°C
(a) 50 (b) 1−Linear Fresnel lens (c)
50 °C 50 °C
2−The STEG devices
45 45
3−Electrolytic cell 60 H2
45
O2
Production (µmol)
40 40
4−Graphite electrode
35 35 5−Platinum plate electrode
30 30 40 Light
25 i ii 25
40
35 1
50 °C 50 °C
O2 H2 5
45 45
30 (+) 4 20
40 40
35 35
30 30 25 3
2
25 iii iv 25 0
(−) 10:40 11:40 12:40 13:40
Time
(d) I °C (e) (f) 1.0 1.0
93
86
O2 production (mmol)
H2 production (mmol)
0.8 0.8
79
72 0.6 0.6
cathode anode
65
O2 H2 0.4 0.4
58
II 51 0.2 0.2
III
44 FeNi LDHs/CFC Ni Nanosheets
37 + − + − 0.0 0.0
cold sink
0 5 10 15 20 25 30
30 heat sink
Time (min)
Fig.  11 a Temperature distributions under 1 sun irradiation of: (i) hot side and (ii) cold side of bare generator; (iii) hot side and (iv) cold side of
CNP generator. Inserts: temperature statistics of the area in corresponding dotted box, b schematic of the overall water splitting system driven
by 6 series-wound STEG devices, c production of H2 and O2 by the water splitting system at different time. Reproduced with permission from
Ref. [156]. Copyright 2018 Elsevier Inc., d the infrared thermal images of Al2O3 ceramic chip (I) and Al2O3 ceramic chip with Ni film (II) and
Ni nanosheets/Ni film (III), e illustration of electrolyzer-TE hybrid device, f H2/O2 production versus time curve of electrolyzer-TE hybrid device
with additional 0.7 V applied voltage. Reproduced with permission from Ref. [157]. Copyright 2019 Elsevier Inc
was served as electrocatalysts and light absorption layer. conductivity and the thermal conductivity [158]. Consid-
Replacing the conventional power supply, the output volt- ering these factors, the energy conversion efficiency of
age of this integrated system could be immediately applied TE device (5–10%) is low, compared to PVs (up to 46%)
for electrolysis of water. It was demonstrated that the Ni [159]. Therefore, several researches have demonstrated
nanosheets array was utilized as an effective photothermal that by combing TE and PEC reaction, the utilization
conversion layer to generate temperature difference (ΔT) for efficiency for both solar energy harvest and water split-
TE, and as an efficient electrocatalysts for HER (Fig. 11d, ting can reach a high content [160]. The first proposed the
e). The electrolyzer-TE complex devices were constructed combination of PEC and photothermal-electrochemical
for overall water splitting in a two-electrode system, with cycles for H2 production by solar energy was by Nikola
a H2 and O2 production rate of 1.818 and 0.912 mmol h−1, Getoff in 1984 [161], which was in acid aqueous solution
respectively (Fig. 11f). The integrated TE device provided using I2 and I3− acting as a sensitizer with the existence of
great advantages for constructing the water splitting system, ferrous ions. With the introduction of the TE device, the
which were conducive to utilize the solar thermal energy and unabsorbed light was collected to provide heat for partly
the waste heat in the prospective applications [157]. converting into electricity by the TE device. Hence, the
efficiency of H2 production increased of 30% compared
with that of single PEC cycle. However, no research for
5.2 By Integrated Photoelectrochemical‑Thermoelectric
photothermal-electrochemical water splitting was con-
Device
ducted for a long time since then, until 2015, Lee’s group
[126, 162] continuously published two articles to study
The parameters that effect TE conversion efficiency are
the integrated PEC-TE device for water splitting by using
the Seebeck coefficient (or thermopower), the electrical

(a) (b) (c)

Photoelectrochemical Cell
p-type n-type water
H2 water
metal
E0(H+/H2)
E0(H+/H2)
O2 Eg=1.12 eV
ΔG0 qVTE
=1.23 eV p-type Si
p-type Si E0(H 2O/O2)

metal metal
E0(H2O/O2)
Thermoelectric generator Thermoelectric Photoelectrochemical cell

device
(d) (e) 1 Hybrid energy cell (f) 0.4

Cu Experiment data
2 Fitting
PA Cathode
0.3
Volume (mL)
TENG PFA Li-ion
battery
3
H2
Cu collection
Anode
0.2
tube
0.1
Thermoelectric Cell
Water Solution
0.0
0 200 400 600 800 1000
Time (s)
Fig.  12 a Schematic diagram of a PEC-TE hybrid device. Energy band diagrams of b sole PEC and c a PEC-TE hybrid circuit under illumina-
tion depicting the influence of qVTE. Reproduced with permission from Ref. [162]. Copyright 2015 Elsevier Inc., d schematic diagram of the
fabricated TENG-TE hybrid energy cell, e schematic diagram of the self-powered system for water splitting to produce H
2, f produced volume of
H2 at different working times. Reproduced with permission from Ref. [164]. Copyright 2013 Royal Society of Chemistry
solar energy and waste heat energy to generate storable the Fermi level of counter electrode could be adjusted
and transportable H 2 fuel. By using the hybrid water split- by the applied V TE. When the working electrode (p-Si)
ting device water splitting system, the power generation and counter electrode (Pt) were linked to the positive and
for H2 evolution of 55 mW cm−2 was achieved, which was negative terminal of the TE device, respectively, electrons
almost 4 times higher than that of a sole PEC cell. Accord- injected from the Pt counter electrode flew through the
ing to the total charge transferred, the measured volume wire to the anode of the TE device. It was worth noting
of H 2 was well consistent with the theoretical value of that the Fermi energy level moved downward to a more
100% Faraday efficiency (FE), indicating that the gener- positive potential until the Fermi energy level of Pt was
ated charge was completely involved in promoting H2 evo- in alignment with that of the TE device (Fig. 12c). Since
lution. Furthermore, this hybrid operation did not need to the Fermi level of the metal was lower than the oxida-
use noble metals (e.g., platinum or iridium) because the tion potential of the water, the water would spontane-
thermovoltage sole could counteract the kinetic overpoten- ously oxidize under the action of the VTE [162]. Wang
tial [126]. Meanwhile, the author explained the enhance- et al. proposed a novel PV-TE hybrid device consisted of
ment of water splitting in terms of adjusting the Fermi a serial DSSC, a solar selective absorber (SSA) and a TE
level of the counter electrode with ΔT (Fig. 12a–c). As we generator, providing some inspiration for the development
all known, band edge potentials of semiconductors must of high-performance PV-TE hybrid devices. The author
straddle the redox potentials of H 2 and O
2 for full PEC proposed that the sunlight could be separated into two
operation without external bias. However, since the mini- beams, and UV–visible light was absorbed by a solar cell
mum valence band of silicon was not enough positive to and infrared light was absorbed by a TE generator to con-
oxidize water, silicon was not suitable as a semiconductor vert into electricity in this hybrid device, which improve
material for spontaneous water splitting (Fig. 12b) [162]. the overall conversion efficiency greater than 13%. And
Thus, since a TE device was concatenated to a PEC cell, thereafter, water splitting driven by TE device integrated
13
PV cell or other electric generation system was widely [167–171]. Then the produced potential difference would
studied by researchers [163]. Wang’s group manufactured prompt the flow of electrons/ions in the external circuit;
a hybrid energy cell integrated by a TENG, a solar cell and hence, it could be utilized as power source [168, 172–178].
a TE device, which could be utilized for concurrently/sep- In 2014, Tang et al. [172] developed a self-powered hybrid
arately harvesting mechanical, solar and/or thermal ener- system by combining a water-driven TENG with a water
gies. The output power of the hybrid energy cell could be splitting cell (Fig. 13a). The circuit diagram of the split-
immediately utilized to split water with no external power ting system and the structure of disk TENG are shown in
supply (Fig. 12d–f). The volume of the H 2 production Fig. 13b. When the rotated speed of the assembled TENG
was linearly related to the splitting time at a generating was 600 rpm, the formation rate of H2 in the system reached
rate of 4 × 10−4 mL s−1 (Fig. 12f). As shown in Fig. 12e, to 6.25 × 10−3 mL min−1 in the 30 wt% KOH solution. This
there were two ways to water splitting. After the point “1” research provided a strategy of TENG-driven water splitting
was concatenated to the point “3,” this hybrid energy cell for H2 generation without external power source. In 2017,
could be immediately utilized for water splitting, in which the same group prepared a connected TENG-PEC hybrid
the solar cell is in parallel with the rectified TENG. For cell based on a T iO2 photoanode, utilizing a flexible TENG
another way, after the point “1” connecting to the point to collect environmental dynamic energy, and then charging
“2,” the generated energy could be stored in the Li-ion the Li-ion battery to drive water splitting (Fig. 13c, d) [173].
battery and then utilized for electrolysis of water [164]. In the meanwhile, this research proved that the electric field
Intensive research has been conducted to combine PEC provided by TENG-charged battery played an important role
cell and TE device for improved solar H 2 production. How- in electrolysis, as well as improved the utilization efficiency
ever, all of these studies adopt the strategy of connecting PV of solar energy by boosting the photocurrent (Fig. 13e).
cells, TE devices and water splitting electrodes together in Therefore, the TENG-PEC hybrid cell provided an easy and
series. The resulting structure is very complex and not inte- effective method to synergistically transform mechanical and
grated. Therefore, it is a qualitative leap to study how to real- solar energy into chemical energy. Coincidentally, Zhong
ize the integration of photodriving components and water et al. also developed a self-powered PEC water decomposi-
splitting components, no matter for effective use of solar tion system that was combined with a rotatory disk-shaped
energy or for water splitting. The research for integrated TENG (RD-TENG), while a titanium modified hematite
device will offer enormous advantages in the aspect of (Ti–Fe2O3) was used as the photoanode [168]. It is noted
designing the overall water splitting system with integrated that different rotation speed of TENG had different effects
structure which are conducive to the practical applications. on the output peak current change under illumination and in
In addition, the development of an excellent hybrid device dark. When at a low rotation speed, the peak current under
which can realize long-term durability of solar water split- illumination prominently increased in comparison with that
ting will also become a top priority in the further studies. in the dark, while no significant variety at a high rotation
speed, indicating the direct electrolysis of water at a high
6 Water Splitting Driven by a Triboelectric speed.
Besides the water-driven TENG, wind-driven TENG
Nanogenerator
was also widely investigated [179–183]. For example, Fan
As depicted in Sects. 4 and 5, water splitting driven by a et al. demonstrated a coaxial rotatory freestanding TENG
hybrid energy cell including a PV cell or a TE cell (Fig. 12) (CRF-TENG) for collecting wind energy using electrospin-
paves the way for water splitting driven by other energy ning polyvinylidene fluoride (PVDF) nanofiber membrane
devices. Ever since the discovery of TENG by Wang’s group as triboelectric material (Fig. 14a–c) [12]. And on this
in 2012, TENG had been utilized as an external power sup- basis, a fully self-powered system based on CRF-TENG
ply for water splitting [165, 166]. In terms of energy con- for water splitting to produce H2 was proposed. When the
wind speed was 10 m s−1, the H 2 production rate reached
version of TENG, the transfer of contact-induced charges −1
6.9685 μL min in 1.0 M KOH solution (Fig. 14d, e).
between two triboelectric materials with opposite polarity
produced a potential difference during the separation of them

(a) (b)
TENG
Water-
Transformer & driven
Rectifier TENG 1000 µF
KOH
FR4 Copper Kapton Gold
(c) (d)
Photocurrent density (mA cm−2)

TENG + −
(e) > 420 nm 0.5 V
0.12 0V
Transformer
& Rectifier
0.08
n e− H2O/H2
atio
di
Ra
H2 0.04
O2/H2O
H2O
Photoanode
h+ 0.00
Counter electrode charge semiconductor electrolyte counter 0 50 100 150 200
collector electrode Time (s)
Fig.  13 a Schematic diagram of the TENG-driven water splitting system, b the circuit diagram of the splitting system and the structure of disk
TENG. Reproduced with permission from Ref. [172]. Copyright 2014 John Wiley and Sons, c schematic diagram of the TENG-PEC hybrid
cells, d illustration of simplified energy diagram for n-type semiconductor-based solar water splitting, e photocurrent of as-prepared Au-deco-
rated TiO2 with different bias. Reproduced with permission from Ref. [173]. Copyright 2017 John Wiley and Sons
7 Water Splitting Driven by Other Devices cycles. The schematic diagram of the device was utilized
to realize the water splitting with the externally positioned
Recently, water splitting driven by pyroelectric element pyroelectric materials (Fig. 15a). As known, the change of
attracts much attention for it provides an alternative ferroelectric polarization with time during thermal cycling
approach to generate H 2 from instantaneous low-grade was the driving force for the generation of pyroelectric
waste heat or natural temperature variations [184–188]. charge during hot–cold fluctuations. Thus, the influences
For instance, Xie and Brown et al. proposed to apply pyro- of the electrolyte concentration and heating–cooling fre-
electric effect to produce a large enough electric potential quency on the performance of pyroelectric H 2 generation
between two electrodes for water splitting into H 2 and O2 were studied (Fig. 15b–d). As demonstrated, the thickness
gas. The materials utilized in the pyroelectric water split- and the area of PZT sheet played an important role in driv-
ting system were lead zirconate titanate (PZT-5H) and ing water splitting, where the thickness could be used to
PVDF thin film [184]. Zhang et al. proposed a pyroelec- guarantee an enough potential to initiate water splitting
tric water splitting system by utilizing bulk lead PZT as and the area should be maximized to collect the maximal
an external charge supply that underwent hot–cold thermal amount of available surface charge [185]. Therefore, future
13
(a) Self-powered water splitting Gas circulation system Gas chromatograph
− +
Rectifier
~ ~
Transformer
Air Valve
Pressure
Gauge
e− O2 H2 e−
H2O OH− Carrier Gas (N2)
OH− H2O
Circulating Pump
(b) 15 (c) 3
4 m s−1 4 m s−1
10 6 m s−1 2 6 m s−1
Output current (mA)

8 m s−1 8 m s−1
Output voltage (V)
5 10 m s−1 1 10 m s−1
0 0
−5 −1
−10 −2
−15 −3
0 1 2 3 4 0 1 2 3 4
Time (s) Time (s)
(e) 10
(d)
H2 production rate (µL min−1)
500 6 m s−1
8 m s−1 8
400 10 m s−1
6.9685 µL min−1
Volume (µL)
300 6
200 4 3.4705 µL min−1
100
2 1.4151 µL min−1
0
0
0 10 20 30 40 50 60 70 80 6 8 10
Time (min) Wind speed (m s−1)
Fig.  14 a Schematic diagram of CRF-TENG wind energy harvester driven self-powered water splitting system, b the output voltage and c the
output current of the CRF-TENG wind energy harvester with a transformer at different wind speeds, d H2 production volume as a function of
the work times, e H2 production rate of the CRF-TENG with transformer at different wind speeds. Reproduced with permission from Ref. [12].
Copyright 2018 Elsevier Inc
work could concentrate on the formation of pyroelectric high temperatures and high pressures were essential, and
nanostructures to enlarge the surface area of the pyroelec- H2 contamination containing C O2, CH4 and residual CO
tric element or exploring the high heat transfer rates of was inevitable [200–204]. Herein, Bao et al. reported a
other pyroelectric materials to increase the magnitude and novel electrochemical water–gas shift (EWGS) process for
speed of temperature changes [189–192]. directly producing H2 with the purity of over 99.99% and
WGS reaction was a main way for industrial H 2 pro- the FE of approximately 100% under mild conditions. In
duction [193–199]. For the traditional WGS reaction, contrast to the electrocatalytic water splitting, this WGS

(a) (b) 30
20
Polarization (µC cm−2)

ΔT
10
+ −
0
−10
Surface charges −20

ΔT
PZT sheet ΔPs
Surface charges
O2 H2 −30
−60 −30 0 30 60
Electric field (kV cm−1)
(c) 4.5 (d) 4 0.75
4.0
3.5
H2 evolution (µmol)
3
3.0 0.50
Gas (µmol)
Gas (µmol)
2.5 H2 H2
2
2.0
1.5 0.25
1.0 1 O2 O2
0.5
0.0 0 0.00
1 2 3 4 5 6
Time (h)
Fig.  15 a Schematic of pyroelectric as an external source for water splitting, b polarization–electric field loop of PZT sheet and schematic of the
surface pyroelectric charges, c H2 evolution from external pyroelectric water splitting with working time from 1 to 6 h, d the amount and evolu-
tion rate of H
2 and O
2 after 6 h detected from the gas chromatography. Reproduced with permission from Ref. [185]. Copyright 2020 Elsevier
Inc
reaction afforded a promising alternative way to produce Anode∶ CO + 4OH− → CO2− + 2H2 O + 2e−
3
with very low operating voltage, which was realized by the Cathode∶ 2H2 O + 2e → H2 + 2OH−
−
rational design of electrolytic cell and electrocatalysts. In Total∶ CO + 2OH− → H2 + CO2−

3
the WGS reaction process of electrolytic cell, CO was oxi-
dized on the anode and H2 was produced from H2O reduc-
tion on the cathode (Fig. 16a). Meanwhile, anion exchange
membrane was used to separate the cathode and anode, 8 Outlook and Future Challenges
maintain the balance of electrolyte ion concentration and
prevent the cross-contamination of the anodic ( CO2) and H2 is one of the most sustainable and environmental-friendly
cathodic (H2) reaction products in the system. Through energies for replacing fossil fuel energy to mitigate the
optimization of the anode structure by the hydrophobic growing serious energy crisis. In this review, a variety of
PTFE layer on catalyst and design of the anode P t3Cu cata- green energy systems developed for efficient H 2 production
lyst, the water-free compartments at the interface of PTFE are summarized. The matured two-electrode electrolysis of
and catalyst to facilitate the diffusion of CO and weaken water system can realize overall water splitting with a high
interaction between CO and anode catalyst surface by Cu performance at a low cell voltage and long-term stabilities,
were performed (Fig. 16b–d). Finally, directly producing due to the massive efforts on designing and developing of
H2 with the purity of over 99.99% and the FE of approxi- the bifunctional electrocatalysts with excellent electrocata-
mately 100% under mild conditions by this novel electrolytic performance. And many green systems containing
lytic cell was realized [205]. photoelectrodes, solar cells, TE devices, TENG devices,
13
(a)
CO H 2O H2
CO
Anode
Cathode
1~6 MPa 0.1 MPa CO32−
180~250 °C 25 °C
CO
H2 mixture 99.99% H2
CO CO2 OH−
CH4 H2O PTFE
Anion exchange
H2 membrane Catalyst
WGS VS. EWGS Ni wire
(b) 0.5
H2 production (mmol h−1 gcat−1)

(c) 150 (d)
H2O adsorption (mmol g−1)
Without PTFE 100

With PTFE
Faradic efficiency (%)

0.4 0.11 120 Pt@CNTs
80
Pt2.7Cu@CNTs
Water 0.3
Hydrophobic 90 60
PTFE surface
0.2 60 40
CO 0.07
0.1 30 20
Pt Surface
0.0 0 0
Pt/C Pt@CNTs 0.4 0.6 0.8
Potential (V versus RHE)
Fig.  16 a Schematic illustration of the EWGS process in comparison with the traditional WGS process, b schematic diagram of solid/liquid/gas
interfaces on the PTFE-decorated Pt surface, c adsorption of H 2O at 25 °C on Pt/C and Pt@CNTs with and without PTFE treatment detected by
intelligent gravimetric analyzer, d the rate of H
2 production and FE on the cathode at different potentials with the P
t2.7Cu@CNTs and Pt@CNTs
as the anode catalysts. Reproduced with permission from Ref. [205]. Copyright 2019 Springer Nature
pyroelectric devices, and EWGS devices can efficiently uti- active non-noble metal catalysts for HER and OER in PEM
lize renewable energy for water splitting with lower or even water electrolyzer is the key thing that needs to be strength-
no external power source. Therefore, the development of ened. Secondly, many developed low-cost catalysts for alka-
green energy system is significant for utilizing the renewable line water splitting are unable to meet the requirements of
energy for water splitting. high current density and long-term stability in industrial
Although many important developments have been made applications. As a consequence, the development of high
for green energy systems powered water splitting, this field stability, abundant active sites and large size of electrode
also faces some challenges. Firstly, most non-noble metal for HER and OER is crucial for industrial applications.
bifunctional catalysts for water splitting show excellent Thirdly, utilizing the photovoltaic device/TE devices/pyro-
performance only in the alkaline electrolytes, while rare electric devices/TENG devices to convert solar energy/ther-
low-cost catalysts for water splitting can work well in the mal energy/wind energy/water energy to electrical energy
acidic electrolytes. With the introduction of PEM in acidic for delivering water splitting is a promising way to achieve
electrolytes, the utilization of low-cost catalysts for water renewable energy driven H2 production. However, the pho-
splitting is attractive. Therefore, the development of highly tovoltaic device/TE devices/pyroelectric devices/TENG

devices in tandem with an electrolyzer will obviously 3. B. You, Y. Sun, Innovative strategies for electrocatalytic
increase the cost for H
2 production. Therefore, improving water splitting. Acc. Chem. Res. 51(7), 1571–1580 (2018).
https://doi.org/10.1021/acs.accounts.8b00002
the compatibility of devices and the integrity of systems by
4. W. Wang, M. Xu, X. Xu, W. Zhou, Z. Shao, Perovskite oxide
integrated the photovoltaic device/TE devices/pyroelectric based electrodes for high-performance photoelectrochemi-
devices/TENG devices with an electrolyzer into a single cal water splitting. Angew. Chem. Int. Ed. 59(1), 136–152
system will decrease the overall cost for H2 production in (2020). https://doi.org/10.1002/anie.201900292
future practical application. 5. K. Oka, O. Tsujimura, T. Suga, H. Nishide, B. Winther-
Jensen, Light-assisted electrochemical water-splitting at very
During the past few years, the different driven systems low bias voltage using metal-free polythiophene as photo-
for water splitting have made great progress and many cathode at high pH in a full-cell setup. Energy Environ. Sci.
exciting achievements. With the incessant efforts that are 11(5), 1335–1342 (2018). https://doi.org/10.1039/C7EE0
3669H
being devoted to this field, water splitting driven by green
6. S.Y. Tee, K.Y. Win, W.S. Teo, L.D. Koh, S. Liu, C.P. Teng,
energy systems will make a significant contribution to
M.Y. Han, Recent progress in energy-driven water splitting.
large-scale practical applications of clean energy systems Adv. Sci. 4(5), 1600337 (2017). https://doi.org/10.1002/
in the near future. We hope this review will encourage advs.201600337
more efforts into the development of novel green energy 7. S. Anantharaj, S.R. Ede, K. Karthick, S. Sam Sankar, K. San-
geetha, P.E. Karthik, S. Kundu, Precision and correctness
system for hydrogen energy production to realize the
in the evaluation of electrocatalytic water splitting: revisit-
whole process with low cost, pollution-free and energy ing activity parameters with a critical assessment. Energy
sustainability conversion in practical applications. Environ. Sci. 11(4), 744–771 (2018). https: //doi.org/10.1039/
C7EE03457A
Acknowledgements This work was supported by Taishan Scholars 8. J. Yu, G. Li, H. Liu, L. Zhao, A. Wang et al., Ru–Ru2PФNPC
Project Special Funds (tsqn201812083), Natural Science Founda- and NPC@RuO2 synthesized via environment-friendly and
tion of Shandong Province (ZR2019YQ20, 2019JMRH0410) and solid-phase phosphating process by saccharomycetes as N/P
the National Natural Science Foundation of China (51972147). sources and carbon template for overall water splitting in acid
electrolyte. Adv. Funct. Mater. 29(22), 1901154 (2019). https
Open Access This article is licensed under a Creative Commons ://doi.org/10.1002/adfm.201901154
Attribution 4.0 International License, which permits use, sharing, 9. C. Guan, W. Xiao, H. Wu, X. Liu, W. Zang et al., Hollow Mo-
adaptation, distribution and reproduction in any medium or format, doped CoP nanoarrays for efficient overall water splitting.
as long as you give appropriate credit to the original author(s) and Nano Energy 48, 73–80 (2018). https://doi.org/10.1016/j.
the source, provide a link to the Creative Commons licence, and nanoen.2018.03.034
indicate if changes were made. The images or other third party 10. H. Wu, X. Lu, G. Zheng, G.W. Ho, Topotactic engineering of
material in this article are included in the article’s Creative Com- ultrathin 2D nonlayered nickel selenides for full water elec-
mons licence, unless indicated otherwise in a credit line to the trolysis. Adv. Energy Mater. 8(14), 1702704 (2018). https://
material. If material is not included in the article’s Creative Com- doi.org/10.1002/aenm.201702704
mons licence and your intended use is not permitted by statutory
11. S. Chu, A. Majumdar, Opportunities and challenges for a sus-
regulation or exceeds the permitted use, you will need to obtain
tainable energy future. Nature 488(7411), 294–303 (2012).
permission directly from the copyright holder. To view a copy of
https://doi.org/10.1038/nature11475
this licence, visit http://creativecommons.org/licenses/by/4.0/.
12. X. Ren, H. Fan, C. Wang, J. Ma, H. Li, M. Zhang, S. Lei,
W. Wang, Wind energy harvester based on coaxial rotatory
freestanding triboelectric nanogenerators for self-powered
water splitting. Nano Energy 50, 562–570 (2018). https://
References doi.org/10.1016/j.nanoen.2018.06.002
13. I. Roger, M.A. Shipman, M.D. Symes, Earth-abundant cata-
1. E. Hu, Y. Feng, J. Nai, D. Zhao, Y. Hu, X.W. Lou, Construc-
lysts for electrochemical and photoelectrochemical water
tion of hierarchical Ni–Co–P hollow nanobricks with ori-
splitting. Nat. Rev. Chem. 1(1), 0003 (2017). https://doi.
ented nanosheets for efficient overall water splitting. Energy
org/10.1038/s41570-016-0003
Environ. Sci. 11(4), 872–880 (2018). https: //doi.org/10.1039/
C8EE00076J 14. Z. Wang, C. Li, K. Domen, Recent developments in hetero-
geneous photocatalysts for solar-driven overall water split-
2. F. Yu, H. Zhou, Y. Huang, J. Sun, F. Qin et al., High-per-
ting. Chem. Soc. Rev. 48(7), 2109–2125 (2019). https://doi.
formance bifunctional porous non-noble metal phosphide
org/10.1039/C8CS00542G
catalyst for overall water splitting. Nat. Commun. 9(1), 2551
(2018). https://doi.org/10.1038/s41467-018-04746-z 15. W. Yang, R.R. Prabhakar, J. Tan, S.D. Tilley, J. Moon, Strat-
egies for enhancing the photocurrent, photovoltage, and
stability of photoelectrodes for photoelectrochemical water
13
splitting. Chem. Soc. Rev. 48(19), 4979–5015 (2019). https water splitting. Nat. Commun. 9, 2452 (2018). https://doi.
://doi.org/10.1039/C8CS00997J org/10.1038/s41467-018-04888-0
16. F. Niu, D. Wang, F. Li, Y. Liu, S. Shen, T.J. Meyer, Hybrid 27. D. Jeon, J. Park, C. Shin, H. Kim, J.-W. Jang, D.W. Lee, J.
photoelectrochemical water splitting systems: from inter- Ryu, Superaerophobic hydrogels for enhanced electrochemi-
face design to system assembly. Adv. Energy Mater. 10(11), cal and photoelectrochemical hydrogen production. Sci. Adv.
1900399 (2019). https://doi.org/10.1002/aenm.201900399 6, eaaz3944 (2020). https://doi.org/10.1126/sciadv.aaz3944
17. H. Zhou, F. Yu, Q. Zhu, J. Sun, F. Qin et al., Water split- 28. L. Zeng, L. Yang, J. Lu, J. Jia, J. Yu, Y. Deng, M. Shao,
ting by electrolysis at high current densities under 1.6 volts. W. Zhou, One-step synthesis of Fe–Ni hydroxide nanosheets
Energy Environ. Sci. 11(10), 2858–2864 (2018). https://doi. derived from bimetallic foam for efficient electrocatalytic
org/10.1039/C8EE00927A oxygen evolution and overall water splitting. Chin. Chem.
18. G. Li, J. Yu, J. Jia, L. Yang, L. Zhao, W. Zhou, H. Liu, Lett. 29(12), 1875–1878 (2018). https://doi.org/10.1016/j.
Cobalt–cobalt phosphide nanoparticles@nitrogen–phos- cclet.2018.10.026
phorus doped carbon/graphene derived from cobalt ions 29. J.H. Lin, Y.T. Yan, C. Li, X.Q. Si, H.H. Wang et al., Bifunc-
adsorbed saccharomycete yeasts as an efficient, stable, and tional electrocatalysts based on Mo-doped NiCoP nanosheet
large-current-density electrode for hydrogen evolution reac- arrays for overall water splitting. Nano-Micro Lett. 11, 55
tions. Adv. Funct. Mater. 28(40), 1801332 (2018). https: //doi. (2019). https://doi.org/10.1007/s40820-019-0289-6
org/10.1002/adfm.201801332 30. Y. Yan, B.Y. Xia, B. Zhao, X. Wang, A review on noble-
19. X. Li, J. Yu, J. Jia, A. Wang, L. Zhao, T. Xiong, H. Liu, W. metal-free bifunctional heterogeneous catalysts for overall
Zhou, Confined distribution of platinum clusters on M oO2 electrochemical water splitting. J. Mater. Chem. A 4(45),
hexagonal nanosheets with oxygen vacancies as a high-effi- 17587–17603 (2016). https://doi.org/10.1039/C6TA08075H
ciency electrocatalyst for hydrogen evolution reaction. Nano 31. Y. Ha, L. Shi, Z. Chen, R. Wu, Phase-transited lysozyme-
Energy 62, 127–135 (2019). https://doi.org/10.1016/j.nanoe driven formation of self-supported Co3O4@C nanomeshes
n.2019.05.013 for overall water splitting. Adv. Sci. 6(11), 1900272 (2019).
20. J. Jia, T. Xiong, L. Zhao, F. Wang, H. Liu, R. Hu, J. Zhou, https://doi.org/10.1002/advs.201900272
W. Zhou, S. Chen, Ultrathin n-doped Mo2C nanosheets with 32. K. Chi, X. Tian, Q. Wang, Z. Zhang, X. Zhang et al., Oxy-
exposed active sites as efficient electrocatalyst for hydrogen gen vacancies engineered CoMoO 4 nanosheet arrays as
evolution reactions. ACS Nano 11(12), 12509–12518 (2017). efficient bifunctional electrocatalysts for overall water split-
https://doi.org/10.1021/acsnano.7b06607 ting. J. Catal. 381, 44–52 (2020). https://doi.org/10.1016/j.
21. W. Zhou, J. Lu, K. Zhou, L. Yang, Y. Ke, Z. Tang, S. Chen, jcat.2019.10.025
CoSe2 nanoparticles embedded defective carbon nanotubes 33. Y. Zhang, J. Fu, H. Zhao, R. Jiang, F. Tian, R. Zhang, Tre-
derived from MOFs as efficient electrocatalyst for hydrogen mella-like Ni3S2/MnS with ultrathin nanosheets and abun-
evolution reaction. Nano Energy 28, 143–150 (2016). https dant oxygen vacancies directly used for high speed overall
://doi.org/10.1016/j.nanoen.2016.08.040 water splitting. Appl. Catal. B 257, 117899 (2019). https://
22. L.P. Wen, X.Y. Shan, J. Liu, H.R. Mu, Y. Xiao et al., Engi- doi.org/10.1016/j.apcatb.2019.117899
neered superhydrophilic/superaerophobic electrocatalysts 34. N. Yao, P. Li, Z. Zhou, R. Meng, G. Cheng, W. Luo, Nitro-
composed of supported CoMoSx chalcogels for overall water gen engineering on 3D dandelion-flower-like C oS2 for high-
splitting. Angew. Chem. Int. Ed. 59(4), 1659–1665 (2020). performance overall water splitting. Small 15(31), 1901993
https://doi.org/10.1002/anie.201911617 (2019). https://doi.org/10.1002/smll.201901993
23. N.N. Han, K.R. Yang, Z.Y. Lu, Y.J. Li, W.W. Xu et al., 35. Q. Qin, L. Chen, T. Wei, X. Liu, M oS2/NiS yolk–shell micro-
Nitrogen-doped tungsten carbide nanoarray as an efficient sphere-based electrodes for overall water splitting and asym-
bifunctional electrocatalyst for water splitting in acid. Nat. metric supercapacitor. Small 15(29), 1803639 (2019). https
Commun. 9, 924 (2018). https: //doi.org/10.1038/s41467 -018- ://doi.org/10.1002/smll.201803639
03429-z 36. Y. Yang, K. Zhang, H. Lin, X. Li, H.C. Chan, L. Yang, Q.
24. Z.Y. Lu, W. Zhu, X.Y. Yu, H.C. Zhang, Y.J. Li et al., Gao, MoS2–Ni3S2 heteronanorods as efficient and stable
Ultrahigh hydrogen evolution performance of under-water bifunctional electrocatalysts for overall water splitting. ACS
“Superaerophobic” MoS2 nanostructured electrodes. Adv. Catal. 7(4), 2357–2366 (2017). https://doi.org/10.1021/acsca
Mater. 26(17), 2683–2687 (2014). https://doi.org/10.1002/ tal.6b03192
adma.201304759 37. L. Li, C. Sun, B. Shang, Q. Li, J. Lei, N. Li, F. Pan, Tailoring
25. W. Xu, Z. Lu, X. Sun, L. Jiang, X. Duan, Superwetting elec- the facets of Ni3S2 as a bifunctional electrocatalyst for high-
trodes for gas-involving electrocatalysis. Acc. Chem. Res. performance overall water-splitting. J. Mater. Chem. A 7(30),
51, 1590–1598 (2018). https://doi.org/10.1021/acs.accou 18003–18011 (2019). https://doi.org/10.1039/C9TA05578A
nts.8b00070 38. J. Lin, P. Wang, H. Wang, C. Li, X. Si et al., Defect-rich
26. H.Y. Li, S.M. Chen, Y. Zhang, Q.H. Zhang, X.F. Jia et al., heterogeneous MoS2/NiS2 nanosheets electrocatalysts for effi-
Systematic design of superaerophobic nanotubearray elec- cient overall water splitting. Adv. Sci. 6(14), 1900246 (2019).
trode comprised of transition-metal sulfides for overall https://doi.org/10.1002/advs.201900246

39. Y. Deng, Z. Liu, A. Wang, D. Sun, Y. Chen et al., Oxygen- 50. Y. Wang, C. Xie, D. Liu, X. Huang, J. Huo, S. Wang, Nan-
incorporated MoX (X: S, Se or P) nanosheets via univer- oparticle-stacked porous nickel-iron nitride nanosheet: a
sal and controlled electrochemical anodic activation for highly efficient bifunctional electrocatalyst for overall water
enhanced hydrogen evolution activity. Nano Energy 62, 338– splitting. ACS Appl. Mater. Interfaces. 8(29), 18652–18657
347 (2019). https://doi.org/10.1016/j.nanoen.2019.05.036 (2016). https://doi.org/10.1021/acsami.6b05811
40. T. Zhang, L. Hang, Y. Sun, D. Men, X. Li, L. Wen, X. Lyu, Y. 51. A. Wu, Y. Xie, H. Ma, C. Tian, Y. Gu et al., Integrating the
Li, Hierarchical hetero-Ni3Se4@NiFe LDH micro/nanosheets active OER and HER components as the heterostructures for
as efficient bifunctional electrocatalysts with superior stabil- the efficient overall water splitting. Nano Energy 44, 353–363
ity for overall water splitting. Nanoscale Horiz. 4(5), 1132– (2018). https://doi.org/10.1016/j.nanoen.2017.11.045
1138 (2019). https://doi.org/10.1039/C9NH00177H 52. Y. Hu, D. Huang, J. Zhang, Y. Huang, M.S.J.T. Balogun, Y.
41. H. Sun, J.-G. Li, L. Lv, Z. Li, X. Ao, C. Xu, X. Xue, G. Tong, Dual doping induced interfacial engineering of F e2N/
Hong, C. Wang, Engineering hierarchical CoSe/NiFe layered- Fe3N hybrids with favorable d-band towards efficient overall
double-hydroxide nanoarrays as high efficient bifunctional water splitting. ChemCatChem 11(24), 6051–6060 (2019).
electrocatalyst for overall water splitting. J. Power Sources https://doi.org/10.1002/cctc.201901224
425, 138–146 (2019). https : //doi.org/10.1016/j.jpows 53. Z. Liu, H. Tan, D. Liu, X. Liu, J. Xin et al., Promotion of
our.2019.04.014 overall water splitting activity over a wide pH range by
42. F. Ming, H. Liang, H. Shi, X. Xu, G. Mei, Z. Wang, MOF- interfacial electrical effects of metallic NiCo-nitrides nano-
derived co-doped nickel selenide/C electrocatalysts supported particle/NiCo2O4 nanoflake/graphite fibers. Adv. Sci. 6(5),
on Ni foam for overall water splitting. J. Mater. Chem. A 1801829 (2019). https://doi.org/10.1002/advs.201801829
4(39), 15148–15155 (2016). https://doi.org/10.1039/C6TA0 54. Z. Yuan, J. Li, M. Yang, Z. Fang, J. Jian, D. Yu, X. Chen,
6496E L. Dai, Ultrathin black phosphorus-on-nitrogen doped gra-
43. N. Li, Y. Zhang, M. Jia, X. Lv, X. Li et al., 1T/2H phene for efficient overall water splitting: dual modulation
MoSe2-on-mxene heterostructure as bifunctional electro- roles of directional interfacial charge transfer. J. Am. Chem.
catalyst for efficient overall water splitting. Electrochim. Soc. 141(12), 4972–4979 (2019). https://doi.org/10.1021/
Acta 326, 134976 (2019). https ://doi.org/10.1016/j.elect jacs.9b00154
acta.2019.134976 55. C. Xing, Y. Xue, B. Huang, H. Yu, L. Hui et al., Fluorograph-
44. J. Wang, W. Yang, J. Liu, CoP2 nanoparticles on reduced diyne: a metal-free catalyst for applications in water reduction
graphene oxide sheets as a super-efficient bifunctional elec- and oxidation. Angew. Chem. Int. Ed. 131(39), 14035–14041
trocatalyst for full water splitting. J. Mater. Chem. A 4(13), (2019). https://doi.org/10.1002/anie.201905729
4686–4690 (2016). https://doi.org/10.1039/C6TA00596A 56. C.W. Liang, P.C. Zou, A. Nairan, Y.Q. Zhang, J.X. Liu et al.,
45. Y. Li, H. Zhang, M. Jiang, Q. Zhang, P. He, X. Sun, 3D Exceptional performance of hierarchical Ni–Fe oxyhydrox-
self-supported Fe-doped N i2P nanosheet arrays as bifunc- ide@NiFe alloy nanowire array electrocatalysts for large cur-
tional catalysts for overall water splitting. Adv. Funct. Mater. rent density water splitting. Energy Environ. Sci. 13, 86–95
27(37), 1702513 (2017). https: //doi.org/10.1002/adfm.20170 (2020). https://doi.org/10.1039/c9ee02388g
2513 57. I. Vincent, D. Bessarabov, Low cost hydrogen production
46. H. Sun, Y. Min, W. Yang, Y. Lian, L. Lin et al., Morphologi- by anion exchange membrane electrolysis: a review. Renew.
cal and electronic tuning of N i2P through iron doping toward Sustain. Energy Rev. 81, 1690–1704 (2018). https://doi.
highly efficient water splitting. ACS Catal. 9(10), 8882–8892 org/10.1016/j.rser.2017.05.258
(2019). https://doi.org/10.1021/acscatal.9b02264 58. H. Ju, S. Badwal, S. Giddey, A comprehensive review of car-
47. B. Cao, Y. Cheng, M. Hu, P. Jing, Z. Ma, B. Liu, R. Gao, bon and hydrocarbon assisted water electrolysis for hydrogen
J. Zhang, Efficient and durable 3D self-supported nitrogen- production. Appl. Energy 231, 502–533 (2018). https://doi.
doped carbon-coupled nickel/cobalt phosphide electrodes: org/10.1016/j.apenergy.2018.09.125
Stoichiometric ratio regulated phase- and morphology- 59. C. Panda, P.W. Menezes, M. Zheng, S. Orthmann, M. Driess,
dependent overall water splitting performance. Adv. Funct. In situ formation of nanostructured core-shell C u3N–CuO to
Mater. 29(44), 1906316 (2019). https://doi.org/10.1002/ promote alkaline water electrolysis. ACS Energy Lett. 4(3),
adfm.201906316 747–754 (2019). https: //doi.org/10.1021/acsene rgyle tt.9b000
48. L. Zhang, X. Wang, A. Li, X. Zheng, L. Peng et al., Rational 91
construction of macroporous CoFeP triangular plate arrays 60. J.M. Wei, M. Zhou, A.C. Long, Y.M. Xue, H.B. Liao, C. Wei,
from bimetal-organic frameworks as high-performance Z.J. Xu, Heterostructured electrocatalysts for hydrogen evolu-
overall water-splitting catalysts. J. Mater. Chem. A 7(29), tion reaction under alkaline conditions. Nano-Micro Lett. 10,
17529–17535 (2019). https://doi.org/10.1039/C9TA05282H 75 (2018). https://doi.org/10.1007/s40820-018-0229-x
49. J. Lin, Y. Yan, C. Li, X. Si, H. Wang et al., Bifunctional elec- 61. T. Zhang, K. Yang, C. Wang, S. Li, Q. Zhang et al., Nanomet-
trocatalysts based on Mo-doped NiCoP nanosheet arrays for ric Ni5P4 clusters nested on N iCo2O4 for efficient hydrogen
overall water splitting. Nano-Micro Lett. 11(1), 55 (2019). production via alkaline water electrolysis. Adv. Energy Mater.
https://doi.org/10.1007/s40820-019-0289-6 8(29), 1801690 (2018). https://doi.org/10.1002/aenm.20180
1690
13
62. K. Zhang, M.B. McDonald, I.E.A. Genina, P.T. Hammond, 74. J.C. Bui, J.T. Davis, D.V. Esposito, 3D-printed electrodes for
A highly conductive and mechanically robust O H− conduct- membraneless water electrolysis. Sustain. Energy Fuels 4(1),
ing membrane for alkaline water electrolysis. Chem. Mater. 213–225 (2020). https://doi.org/10.1039/C9SE00710E
30(18), 6420–6430 (2018). https: //doi.org/10.1021/acs. 75. M.I. Gillespie, R.J. Kriek, Hydrogen production from a
chemmater.8b02709 rectangular horizontal filter press divergent electrode-flow-
63. D. Aili, M.R. Kraglund, J. Tavacoli, C. Chatzichristodou- through (DEFT™) alkaline electrolysis stack. J. Power
lou, J.O. Jensen, Polysulfone–polyvinylpyrrolidone blend Sources 372, 252–259 (2017). https: //doi.org/10.1016/j.jpows
membranes as electrolytes in alkaline water electrolysis. J. our.2017.10.080
Membr. Sci. 598, 117674 (2020). https://doi.org/10.1016/j. 76. M.I. Gillespie, R.J. Kriek, Scalable hydrogen production from
memsci.2019.117674 a mono-circular filter press divergent electrode-flow-through
64. P. Fortin, T. Khoza, X. Cao, S.Y. Martinsen, A. Oyarce Bar- alkaline electrolysis stack. J. Power Sources 397, 204–213
nett, S. Holdcroft, High-performance alkaline water electroly- (2018). https://doi.org/10.1016/j.jpowsour.2018.07.026
sis using Aemion™ anion exchange membranes. J. Power 77. A.G. Wallace, M.D. Symes, Decoupling strategies in electro-
Sources 451, 227814 (2020). https://doi.org/10.1016/j.jpows chemical water splitting and beyond. Joule 2(8), 1390–1395
our.2020.227814 (2018). https://doi.org/10.1016/j.joule.2018.06.011
65. M. Carmo, D.L. Fritz, J. Mergel, D. Stolten, A comprehensive 78. J. Wang, L. Ji, X. Teng, Y. Liu, L. Guo, Z. Chen, Decoupling
review on PEM water electrolysis. Int. J. Hydrogen Energy half-reactions of electrolytic water splitting by integrating a
38(12), 4901–4934 (2013). https://doi.org/10.1016/j.ijhyd polyaniline electrode. J. Mater. Chem. A 7(21), 13149–13153
ene.2013.01.151 (2019). https://doi.org/10.1039/C9TA03285A
66. W. Tong, M. Forster, F. Dionigi, S. Dresp, R.S. Erami, P. 79. X. Liu, J. Chi, B. Dong, Y. Sun, Recent progress in decou-
Strasser, A.J. Cowan, P. Farràs, Electrolysis of low-grade pled H2 and O 2 production from electrolytic water splitting.
and saline surface water. Nat. Energy (2020). https://doi. ChemElectroChem 6(8), 2157–2166 (2019). https://doi.
org/10.1038/s41560-020-0550-8 org/10.1002/celc.201801671
67. A. Kovač, D. Marciuš, L. Budin, Solar hydrogen produc- 80. A. Landman, H. Dotan, G.E. Shter, M. Wullenkord, A.
tion via alkaline water electrolysis. Int. J. Hydrogen Energy Houaijia, A. Maljusch, G.S. Grader, A. Rothschild, Pho-
44(20), 9841–9848 (2019). https://doi.org/10.1016/j.ijhyd toelectrochemical water splitting in separate oxygen and
ene.2018.11.007 hydrogen cells. Nat. Mater. 16(6), 646–651 (2017). https://
68. S. Marini, P. Salvi, P. Nelli, R. Pesenti, M. Villa, M. Ber- doi.org/10.1038/nmat4876
rettoni, G. Zangari, Y. Kiros, Advanced alkaline water elec- 81. Y. Ma, X. Dong, Y. Wang, Y. Xia, Decoupling hydrogen
trolysis. Electrochim. Acta 82, 384–391 (2012). https://doi. and oxygen production in acidic water electrolysis using a
org/10.1016/j.electacta.2012.05.011 polytriphenylamine-based battery electrode. Angew. Chem.
69. S. Barwe, B. Mei, J. Masa, W. Schuhmann, E. Ventosa, Int. Ed. 57(11), 2904–2908 (2018). https://doi.org/10.1002/
Overcoming cathode poisoning from electrolyte impurities anie.201800436
in alkaline electrolysis by means of self-healing electro- 82. Y. Ma, Z. Guo, X. Dong, Y. Wang, Y. Xia, Organic proton-
catalyst films. Nano Energy 53, 763–768 (2018). https://doi. buffer electrode to separate hydrogen and oxygen evolution
org/10.1016/j.nanoen.2018.09.045 in acid water electrolysis. Angew. Chem. Int. Ed. 58(14),
70. R. Phillips, A. Edwards, B. Rome, D.R. Jones, C.W. Dunnill, 4622–4626 (2019). https://doi.org/10.1002/anie.201814625
Minimising the ohmic resistance of an alkaline electrolysis 83. H. Dotan, A. Landman, S.W. Sheehan, K.D. Malviya, G.E.
cell through effective cell design. Int. J. Hydrogen Energy Shter et al., Decoupled hydrogen and oxygen evolution by a
42(38), 23986–23994 (2017). https://doi.org/10.1016/j.ijhyd two-step electrochemical–chemical cycle for efficient overall
ene.2017.07.184 water splitting. Nat. Energy 4(9), 786–795 (2019). https: //doi.
71. A. Gabler, C.I. Müller, T. Rauscher, T. Gimpel, R. Hahn org/10.1038/s41560-019-0462-7
et al., Ultrashort-pulse laser structured titanium surfaces 84. W.T. Grubb, Ionic migration in ion-exchange membranes. J.
with sputter-coated platinum catalyst as hydrogen evolution Phys. Chem. 63(1), 55–58 (1959). https://doi.org/10.1021/
electrodes for alkaline water electrolysis. Int. J. Hydrogen j150571a015
Energy 43(15), 7216–7226 (2018). https://doi.org/10.1016/j. 85. E.J. Park, C.B. Capuano, K.E. Ayers, C. Bae, Chemically
ijhydene.2018.02.130 durable polymer electrolytes for solid-state alkaline water
72. J. Zhang, C. Zhang, J. Sha, H. Fei, Y. Li, J.M. Tour, Efficient electrolysis. J. Power Sources 375, 367–372 (2018). https://
water-splitting electrodes based on laser-induced graphene. doi.org/10.1016/j.jpowsour.2017.07.090
ACS Appl. Mater. Interfaces. 9(32), 26840–26847 (2017). 86. M. Zhu, Q. Shao, Y. Qian, X. Huang, Superior overall
https://doi.org/10.1021/acsami.7b06727 water splitting electrocatalysis in acidic conditions enabled
73. S.M.H. Hashemi, P. Karnakov, P. Hadikhani, E. Chinello, by bimetallic Ir–Ag nanotubes. Nano Energy 56, 330–337
S. Litvinov, C. Moser, P. Koumoutsakos, D. Psaltis, A ver- (2019). https://doi.org/10.1016/j.nanoen.2018.11.023
satile and membrane-less electrochemical reactor for the 87. L. Fu, F. Yang, G. Cheng, W. Luo, Ultrathin Ir nanowires as
electrolysis of water and brine. Energy Environ. Sci. 12(5), high-performance electrocatalysts for efficient water splitting
1592–1604 (2019). https://doi.org/10.1039/C9EE00219G

in acidic media. Nanoscale 10(4), 1892–1897 (2018). https:// 100. L.G. Xia, J.H. Li, J. Bai, L.S. Li, S. Chen, B.X. Zhou, BiVO4
doi.org/10.1039/C7NR09377B photoanode with exposed (040) facets for enhanced pho-
88. C. Liu, M. Carmo, G. Bender, A. Everwand, T. Lickert et al., toelectrochemical performance. Nano-Micro Lett. 10, 11
Performance enhancement of PEM electrolyzers through (2018). https://doi.org/10.1007/s40820-017-0163-3
iridium-coated titanium porous transport layers. Electrochem. 101. A. Landman, R. Halabi, P. Dias, H. Dotan, A. Mehlmann
Commun. 97, 96–99 (2018). https://doi.org/10.1016/j.eleco et al., Decoupled photoelectrochemical water splitting sys-
m.2018.10.021 tem for centralized hydrogen production. Joule 4(2), 448–471
89. J.-W. Yu, G.-B. Jung, Y.-J. Su, C.-C. Yeh, M.-Y. Kan, C.-Y. (2020). https://doi.org/10.1016/j.joule.2019.12.006
Lee, C.-J. Lai, Proton exchange membrane water electrolysis 102. J.H. Kim, J.S. Lee, Elaborately modified BiVO4 photoanodes
system-membrane electrode assembly with additive. Int. J. for solar water splitting. Adv. Mater. 31(20), 1806938 (2019).
Hydrogen Energy 44(30), 15721–15726 (2019). https://doi. https://doi.org/10.1002/adma.201806938
org/10.1016/j.ijhydene.2018.11.192 103. E. Edwardes Moore, V. Andrei, S. Zacarias, I.A.C. Pereira,
90. A. Zinser, G. Papakonstantinou, K. Sundmacher, Analysis E. Reisner, Integration of a hydrogenase in a lead halide per-
of mass transport processes in the anodic porous transport ovskite photoelectrode for tandem solar water splitting. ACS
layer in PEM water electrolysers. Int. J. Hydrogen Energy Energy Lett. 5(1), 232–237 (2020). https://doi.org/10.1021/
44(52), 28077–28087 (2019). https://doi.org/10.1016/j.ijhyd acsenergylett.9b02437
ene.2019.09.081 104. M. Chen, Y. Liu, C. Li, A. Li, X. Chang et al., Spatial control
91. W. Xu, K. Scott, The effects of ionomer content on PEM of cocatalysts and elimination of interfacial defects towards
water electrolyser membrane electrode assembly perfor- efficient and robust CIGS photocathodes for solar water split-
mance. Int. J. Hydrogen Energy 35(21), 12029–12037 (2010). ting. Energy Environ. Sci. 11(8), 2025–2034 (2018). https://
https://doi.org/10.1016/j.ijhydene.2010.08.055 doi.org/10.1039/C7EE03650G
92. P. Millet, R. Ngameni, S.A. Grigoriev, V.N. Fateev, Scien- 105. H. Kobayashi, N. Sato, M. Orita, Y. Kuang, H. Kaneko, T.
tific and engineering issues related to PEM technology: water Minegishi, T. Yamada, K. Domen, Development of highly
electrolysers, fuel cells and unitized regenerative systems. efficient CuIn0.5Ga0.5Se2-based photocathode and application
Int. J. Hydrogen Energy 36(6), 4156–4163 (2011). https:// to overall solar driven water splitting. Energy Environ. Sci.
doi.org/10.1016/j.ijhydene.2010.06.106 11(10), 3003–3009 (2018). https://doi.org/10.1039/C8EE0
93. J.E. Bennett, Electrodes for generation of hydrogen and oxy- 1783B
gen from seawater. Int. J. Hydrogen Energy 5(4), 401–408 106. L. Pan, J.H. Kim, M.T. Mayer, M.-K. Son, A. Ummadisingu
(1980). https://doi.org/10.1016/0360-3199(80)90021-X et al., Boosting the performance of C u2O photocathodes for
94. Y. Kuang, M.J. Kenney, Y.T. Meng, W.-H. Hung, Y.J. Liuf unassisted solar water splitting devices. Nat. Catal. 1(6),
et al., Solar-driven, highly sustained splitting of seawater into 412–420 (2018). https://doi.org/10.1038/s41929-018-0077-6
hydrogen and oxygen fuels. Proc. Natl. Acad. Sci. U.S.A. 107. X. Li, M. Jia, Y. Lu, N. Li, Y.-Z. Zheng, X. Tao, M. Huang,
116, 6624–6629 (2019). https://doi.org/10.1073/pnas.19005 Co(OH)2/BiVO4 photoanode in tandem with a carbon-based
56116 perovskite solar cell for solar-driven overall water split-
95. S. Trasatti, Electrocatalysis in the anodic evolution of oxygen ting. Electrochim. Acta 330, 135183 (2020). https://doi.
and chlorine. Electrochim. Acta 29(11), 1503–1512 (1984). org/10.1016/j.electacta.2019.135183
https://doi.org/10.1016/0013-4686(84)85004-5 108. D. Shao, L. Zheng, D. Feng, J. He, R. Zhang et al., T iO2–
96. F. Dionigi, T. Reier, Z. Pawolek, M. Gliech, P. Strasser, P3HT:PCBM photoelectrochemical tandem cells for solar-
Design criteria, operating conditions, and nickel–iron driven overall water splitting. J. Mater. Chem. A 6(9), 4032–
hydroxide catalyst materials for selective seawater electroly- 4039 (2018). https://doi.org/10.1039/C7TA09367E
sis. Chemsuschem 9(9), 962 (2016). https://doi.org/10.1002/ 109. M. Huang, W. Lei, M. Wang, S. Zhao, C. Li, M. Wang, H.
cssc.201501581 Zhu, Large area high-performance bismuth vanadate pho-
97. F.J. Quan, G.M. Zhan, H. Shang, Y.H. Huang, F.L. Jia, L.Z. toanode for efficient solar water splitting. J. Mater. Chem.
Zhang, Z.H. Ai, Highly efficient electrochemical conversion A 8(7), 3845–3850 (2020). https://doi.org/10.1039/C9TA1
of CO2 and NaCl to CO and NaClO. Green Chem. 21, 3256 3715G
(2019). https://doi.org/10.1039/c9gc01099h 110. P. Varadhan, H.-C. Fu, Y.-C. Kao, R.-H. Horng, J.-H. He,
98. X. Long, L. Gao, F. Li, Y. Hu, S. Wei, C. Wang, T. Wang, An efficient and stable photoelectrochemical system with
J. Jin, J. Ma, Bamboo shoots shaped F eVO4 passivated ZnO 9% solar-to-hydrogen conversion efficiency via InGaP/GaAs
nanorods photoanode for improved charge separation/trans- double junction. Nat. Commun. 10(1), 5282 (2019). https://
fer process towards efficient solar water splitting. Appl. doi.org/10.1038/s41467-019-12977-x
Catal. B 257, 117813 (2019). https://doi.org/10.1016/j.apcat 111. V. Andrei, R.L.Z. Hoye, M. Crespo-Quesada, M. Bajada, S.
b.2019.117813 Ahmad, M. De Volder, R. Friend, E. Reisner, Scalable triple
99. J. Li, X. Jin, R. Li, Y. Zhao, X. Wang, X. Liu, H. Jiao, Cop- cation mixed halide perovskite-BiVO4 tandems for bias-free
per oxide nanowires for efficient photoelectrochemical water water splitting. Adv. Energy Mater. 8(25), 1801403 (2018).
splitting. Appl. Catal. B Environ. 240, 1–8 (2019). https: //doi. https://doi.org/10.1002/aenm.201801403
org/10.1016/j.apcatb.2018.08.070
13
112. Y. Chen, X. Feng, Y. Liu, X. Guan, C. Burda, L. Guo, Metal solar cells and promoted by bifunctional bimetallic phosphide
oxide-based tandem cells for self-biased photoelectrochemi- nanowire arrays. J. Mater. Chem. A 6(41), 20076–20082
cal water splitting. ACS Energy Lett. 5(3), 844–866 (2020). (2018). https://doi.org/10.1039/C8TA08116F
https://doi.org/10.1021/acsenergylett.9b02620 124. L. Yao, A. Rahmanudin, N. Guijarro, K. Sivula, Organic
113. X. Wang, W. Gao, Z. Zhao, L. Zhao, J.P. Claverie et al., Effi- semiconductor based devices for solar water splitting.
cient photo-electrochemical water splitting based on hematite Adv. Energy Mater. 8(32), 1802585 (2018). https://doi.
nanorods doped with phosphorus. Appl. Catal. B 248, 388– org/10.1002/aenm.201802585
393 (2019). https://doi.org/10.1016/j.apcatb.2019.02.048 125. J. Yuan, Y. Zhang, L. Zhou, G. Zhang, H.-L. Yip et al.,
114. G.D. Sabba, M.H. Kumar, L.H. Wong, J. Barber, M. Grätzel, Single-junction organic solar cell with over 15% efficiency
N. Mathews, Perovskite–hematite tandem cells for efficient using fused-ring acceptor with electron-deficient core. Joule
overall solar driven water splitting. Nano Lett. 15(6), 3833– 3(4), 1140–1151 (2019). https: //doi.org/10.1016/j.joule
3839 (2015). https://doi.org/10.1021/acs.nanolett.5b00616 .2019.01.004
115. J.H. Kim, Y. Jo, J.H. Kim, J.W. Jang, H.J. Kang et al., Wire- 126. J. Jung, J. Lee, Thermovoltage-driven solar hydrogen for
less solar water splitting device with robust cobalt-catalyzed, commercialized water splitting. SPIE (2015). https://doi.
dual-doped BiVO4 photoanode and perovskite solar cell in org/10.1117/2.1201512.006219
tandem: a dual absorber artificial leaf. ACS Nano 9(12), 127. Y. Xin, X. Kan, L.-Y. Gan, Z. Zhang, Heterogeneous bime-
11820–11829 (2015). https: //doi.org/10.1021/acsnan o.5b038 tallic phosphide/sulfide nanocomposite for efficient solar-
59 energy-driven overall water splitting. ACS Nano 11(10),
116. J. Luo, Z. Li, S. Nishiwaki, M. Schreier, M.T. Mayer et al., 10303–10312 (2017). https: //doi.org/10.1021/acsnan o.7b050
Targeting ideal dual-absorber tandem water splitting using 20
perovskite photovoltaics and C uInxGa1−xSe2 photocathodes. 128. H. Song, S. Oh, H. Yoon, K.-H. Kim, S. Ryu, J. Oh, Bifunc-
Adv. Energy Mater. 5(24), 1501520 (2015). https://doi. tional NiFe inverse opal electrocatalysts with heterojunction
org/10.1002/aenm.201501520 Si solar cells for 9.54%-efficient unassisted solar water split-
117. Y. Qiu, W. Liu, W. Chen, W. Chen, G. Zhou et al., Efficient ting. Nano Energy 42, 1–7 (2017). https://doi.org/10.1016/j.
solar-driven water splitting by nanocone BiVO4-perovskite nanoen.2017.10.028
tandem cells. Sci. Adv. 2(6), e1501764 (2016). https://doi. 129. B. Koo, D. Kim, P. Boonmongkolras, S.R. Pae, S. Byun et al.,
org/10.1126/sciadv.1501764 Unassisted water splitting exceeding 9% solar-to-hydrogen
118. K.P. Sokol, W.E. Robinson, J. Warnan, N. Kornienko, M.M. conversion efficiency by Cu(In, Ga)(S, Se)2 photocathode
Nowaczyk, A. Ruff, J.Z. Zhang, E. Reisner, Bias-free pho- with modified surface band structure and halide perovskite
toelectrochemical water splitting with photosystem II on solar cell. ACS Appl. Energy Mater. 3(3), 2296–2303 (2020).
a dye-sensitized photoanode wired to hydrogenase. Nat. https://doi.org/10.1021/acsaem.9b02387
Energy 3(11), 944–951 (2018). https: //doi.org/10.1038/s4156 130. B. Kim, G.S. Park, Y.J. Hwang, D.H. Won, W. Kim, D.K.
0-018-0232-y Lee, B.K. Min, Cu(In, Ga)(S, Se)2 photocathodes with a
119. J. Brillet, J.-H. Yum, M. Cornuz, T. Hisatomi, R. Solarska, grown-in CuxS catalyst for solar water splitting. ACS Energy
J. Augustynski, M. Graetzel, K. Sivula, Highly efficient Lett. 4(12), 2937–2944 (2019). https: //doi.org/10.1021/acsen
water splitting by a dual-absorber tandem cell. Nat. Photon- ergylett.9b01816
ics 6(12), 824–828 (2012). https://doi.org/10.1038/nphot 131. N. Gaillard, D. Prasher, M. Chong, A. Deangelis, K. Hors-
on.2012.265 ley et al., Wide-bandgap Cu(In, Ga)S2 photocathodes inte-
120. X. Shi, K. Zhang, K. Shin, M. Ma, J. Kwon et al., Unassisted grated on transparent conductive F:SnO 2 substrates for
photoelectrochemical water splitting beyond 5.7% solar-to- chalcopyrite-based water splitting tandem devices. ACS
hydrogen conversion efficiency by a wireless monolithic Appl. Energy Mater. 2(8), 5515–5524 (2019). https://doi.
photoanode/dye-sensitised solar cell tandem device. Nano org/10.1021/acsaem.9b00690
Energy 13, 182–191 (2015). https://doi.org/10.1016/j.nanoe 132. T.J. Jacobsson, V. Fjällström, M. Sahlberg, M. Edoff, T.
n.2015.02.018 Edvinsson, A monolithic device for solar water splitting
121. V. González-Pedro, I. Zarazua, E.M. Barea, F. Fabregat-San- based on series interconnected thin film absorbers reaching
tiago, E. de la Rosa, I. Mora-Seró, S. Giménez, Panchromatic over 10% solar-to-hydrogen efficiency. Energy Environ. Sci.
solar-to-H2 conversion by a hybrid quantum dots–dye dual 6(12), 3676–3683 (2013). https://doi.org/10.1039/C3EE4
absorber tandem device. J. Phys. Chem. C 118(2), 891–895 2519C
(2014). https://doi.org/10.1021/jp4109893 133. T.J. Jacobsson, C. Platzer-Björkman, M. Edoff, T. Edvins-
122. X. Zhou, J. Zhou, G. Huang, R. Fan, S. Ju, Z. Mi, M. Shen, son, CuInxGa1−xSe2 as an efficient photocathode for solar
A bifunctional and stable Ni–Co–S/Ni–Co–P bistratal elec- hydrogen generation. Int. J. Hydrogen Energy 38(35),
trocatalyst for 10.8%-efficient overall solar water splitting. 15027–15035 (2013). https : //doi.org/10.1016/j.ijhyd
J. Mater. Chem. A 6(41), 20297–20303 (2018). https://doi. ene.2013.09.094
org/10.1039/C8TA07197G 134. A.F. Palmstrom, G.E. Eperon, T. Leijtens, R. Prasanna,
123. L. Ma, W. Zhang, P. Zhao, J. Liang, Y. Hu et al., Highly effi- S.N. Habisreutinger et al., Enabling flexible all-perovskite
cient overall water splitting driven by all-inorganic perovskite

tandem solar cells. Joule 3(9), 2193–2204 (2019). https:// solar spectrum splitting photovoltaic cell-thermoelectric gen-
doi.org/10.1016/j.joule.2019.05.009 erator system. Energy Convers. Manag. 174, 65–71 (2018).
135. C. Wang, Z. Song, C. Li, D. Zhao, Y. Yan, Low-bandgap https://doi.org/10.1016/j.enconman.2018.08.038
mixed tin–lead perovskites and their applications in all- 147. G. Li, S. Shittu, X. Ma, X. Zhao, Comparative analysis of
perovskite tandem solar cells. Adv. Funct. Mater. 29(47), thermoelectric elements optimum geometry between pho-
1808801 (2019). https://doi.org/10.1002/adfm.201808801 tovoltaic–thermoelectric and solar thermoelectric. Energy
136. Z. Yang, Z. Yu, H. Wei, X. Xiao, Z. Ni et al., Enhancing 171, 599–610 (2019). https : //doi.org/10.1016/j.energ
electron diffusion length in narrow-bandgap perovskites y.2019.01.057
for efficient monolithic perovskite tandem solar cells. Nat. 148. D. Zhang, Y. Wang, Y. Yang, Design, performance, and
Commun. 10(1), 4498 (2019). https: //doi.org/10.1038/ application of thermoelectric nanogenerators. Small 15(32),
s41467-019-12513-x 1805241 (2019). https://doi.org/10.1002/smll.201805241
137. D. Zhao, C. Chen, C. Wang, M.M. Junda, Z. Song et al., 149. J. Zhang, H. Zhai, Z. Wu, Y. Wang, H. Xie, M. Zhang,
Efficient two-terminal all-perovskite tandem solar cells Enhanced performance of photovoltaic–thermoelectric cou-
enabled by high-quality low-bandgap absorber layers. Nat. pling devices with thermal interface materials. Energy Rep. 6,
Energy 3(12), 1093–1100 (2018). https://doi.org/10.1038/ 116–122 (2020). https://doi.org/10.1016/j.egyr.2019.12.001
s41560-018-0278-x 150. A. Majumdar, Thermoelectricity in semiconductor nano-
138. R. Lin, H. Lei, D. Ruan, K. Jiang, X. Yu, Z. Wang, W. Mai, structures. Science 303(5659), 777 (2004). https: //doi.
H. Yan, Solar-powered overall water splitting system comb- org/10.1126/science.1093164
ing metal-organic frameworks derived bimetallic nanohy- 151. L. Yang, Z.G. Chen, M.S. Dargusch, J. Zou, High perfor-
brids based electrocatalysts and one organic solar cell. mance thermoelectric materials: progress and their applica-
Nano Energy 56, 82–91 (2019). https://doi.org/10.1016/j. tions. Adv. Energy Mater. 8(6), 1701797 (2017). https://doi.
nanoen.2018.10.058 org/10.1002/aenm.201701797
139. X. Liu, Y. Wang, X. Cui, M. Zhang, B. Wang et al., Ena- 152. J.L. Blackburn, A.J. Ferguson, C. Cho, J.C. Grunlan, Carbon-
bling highly efficient photocatalytic hydrogen generation and nanotube-based thermoelectric materials and devices. Adv.
organics degradation via a perovskite solar cell-assisted semi- Mater. 30(11), 1704386 (2018). https://doi.org/10.1002/
conducting nanocomposite photoanode. J. Mater. Chem. A adma.201704386
7(1), 165–171 (2019). https://doi.org/10.1039/C8TA08998A 153. S. Sun, W. Wang, D. Jiang, L. Zhang, J. Zhou, Infrared light
140. J. Luo, J.-H. Im, M.T. Mayer, M. Schreier, M.K. Nazeer- induced photoelectrocatalytic application via graphene oxide
uddin et al., Water photolysis at 12.3% efficiency via per- coated thermoelectric device. Appl. Catal. B 158–159, 136–
ovskite photovoltaics and earth-abundant catalysts. Science 139 (2014). https://doi.org/10.1016/j.apcatb.2014.04.009
345(6204), 1593 (2014). https: //doi.org/10.1126/scien 154. S.A. Shankaregowda, R.F.S.M. Ahmed, C.B. Nanjegowda, J.
ce.1258307 Wang, S. Guan et al., Single-electrode triboelectric nanogen-
141. A. Kumar, D.K. Chaudhary, S. Parvin, S. Bhattacharyya, erator based on economical graphite coated paper for harvest-
High performance duckweed-derived carbon support to ing waste environmental energy. Nano Energy 66, 104141
anchor NiFe electrocatalysts for efficient solar energy (2019). https://doi.org/10.1016/j.nanoen.2019.104141
driven water splitting. J. Mater. Chem. A 6(39), 18948– 155. X. Huang, W. Zhang, G. Guan, G. Song, R. Zou, J. Hu,
18959 (2018). https://doi.org/10.1039/C8TA06946H Design and functionalization of the NIR-responsive photo-
142. R. Merienne, J. Lynn, E. McSweeney, S.M. O’Shaughnessy, thermal semiconductor nanomaterials for cancer theranos-
Thermal cycling of thermoelectric generators: the effect of tics. Acc. Chem. Res. 50(10), 2529–2538 (2017). https://doi.
heating rate. Appl. Energy 237, 671–681 (2019). https://doi. org/10.1021/acs.accounts.7b00294
org/10.1016/j.apenergy.2019.01.041 156. X. Zhang, W. Gao, X. Su, F. Wang, B. Liu, J.-J. Wang, H.
143. Y. Liu, N. Sun, J. Liu, Z. Wen, X. Sun, S.-T. Lee, B. Sun, Inte- Liu, Y. Sang, Conversion of solar power to chemical energy
grating a silicon solar cell with a triboelectric nanogenerator based on carbon nanoparticle modified photo-thermoelectric
via a mutual electrode for harvesting energy from sunlight generator and electrochemical water splitting system. Nano
and raindrops. ACS Nano 12(3), 2893–2899 (2018). https:// Energy 48, 481–488 (2018). https://doi.org/10.1016/j.nanoe
doi.org/10.1021/acsnano.8b00416 n.2018.03.055
144. L. Xu, Y. Xiong, A. Mei, Y. Hu, Y. Rong, Y. Zhou, B. Hu, H. 157. L. Zhao, Z. Yang, Q. Cao, L. Yang, X. Zhang et al., An earth-
Han, Efficient perovskite photovoltaic–thermoelectric hybrid abundant and multifunctional Ni nanosheets array as electro-
device. Adv. Energy Mater. 8(13), 1702937 (2018). https:// catalysts and heat absorption layer integrated thermoelectric
doi.org/10.1002/aenm.201702937 device for overall water splitting. Nano Energy 56, 563–570
145. G. Li, S. Shittu, T.M.O. Diallo, M. Yu, X. Zhao, J. Ji, A (2019). https://doi.org/10.1016/j.nanoen.2018.11.035
review of solar photovoltaic–thermoelectric hybrid system 158. L. Huang, J. Chen, Z. Yu, D. Tang, Self-powered tempera-
for electricity generation. Energy 158, 41–58 (2018). https:// ture sensor with seebeck effect transduction for photother-
doi.org/10.1016/j.energy.2018.06.021 mal-thermoelectric coupled immunoassay. Anal. Chem.
146. Z. Yang, W. Li, X. Chen, S. Su, G. Lin, J. Chen, Maximum 92(3), 2809–2814 (2020). https://doi.org/10.1021/acs.analc
efficiency and parametric optimum selection of a concentrated hem.9b05218
13
159. V. Andrei, K. Bethke, K. Rademann, Thermoelectricity in the 171. P. Cheng, Y. Liu, Z. Wen, H. Shao, A. Wei et al., Atmos-
context of renewable energy sources: joining forces instead pheric pressure difference driven triboelectric nanogen-
of competing. Energy Environ. Sci. 9(5), 1528–1532 (2016). erator for efficiently harvesting ocean wave energy. Nano
https://doi.org/10.1039/C6EE00247A Energy 54, 156–162 (2018). https://doi.org/10.1016/j.nanoe
160. J.-Y. Jung, D.W. Kim, D.-H. Kim, T.J. Park, R.B. Wehrspohn, n.2018.10.007
J.-H. Lee, Seebeck-voltage-triggered self-biased photoelec- 172. W. Tang, Y. Han, C.B. Han, C.Z. Gao, X. Cao, Z.L. Wang,
trochemical water splitting using HfOx/SiOx bi-layer pro- Self-powered water splitting using flowing kinetic energy.
tected Si photocathodes. Sci. Rep. 9(1), 9132 (2019). https:// Adv. Mater. 27(2), 272–276 (2015). https://doi.org/10.1002/
doi.org/10.1038/s41598-019-45672-4 adma.201404071
161. N. Getoff, Basic problems of photochemical and photo- 173. T. Li, Y. Xu, F. Xing, X. Cao, J. Bian, N. Wang, Z.L. Wang,
electrochemical hydrogen production from water. Int. J. Boosting photoelectrochemical water splitting by TENG-
Hydrogen Energy 9(12), 997–1004 (1984). https: //doi. charged Li-ion battery. Adv. Energy Mater. 7(15), 1700124
org/10.1016/0360-3199(84)90171-X (2017). https://doi.org/10.1002/aenm.201700124
162. S.-M. Shin, J.-Y. Jung, M.-J. Park, J.-W. Song, J.-H. Lee, 174. H. Askari, A. Khajepour, M.B. Khamesee, Z.L. Wang,
Catalyst-free hydrogen evolution of Si photocathode by Embedded self-powered sensing systems for smart vehi-
thermovoltage-driven solar water splitting. J. Power Sources cles and intelligent transportation. Nano Energy 66, 104103
279, 151–156 (2015). https : //doi.org/10.1016/j.jpows (2019). https://doi.org/10.1016/j.nanoen.2019.104103
our.2015.01.020 175. W. Tang, B.D. Chen, Z.L. Wang, Recent progress in power
163. N. Wang, L. Han, H. He, N.-H. Park, K. Koumoto, A novel generation from water/liquid droplet interaction with solid
high-performance photovoltaic–thermoelectric hybrid device. surfaces. Adv. Funct. Mater. 29(41), 1901069 (2019). https
Energy Environ. Sci. 4(9), 3676–3679 (2011). https://doi. ://doi.org/10.1002/adfm.201901069
org/10.1039/C1EE01646F 176. H. Yang, M. Deng, Q. Zeng, X. Zhang, J. Hu et al., Poly-
164. Y. Yang, H. Zhang, Z.-H. Lin, Y. Liu, J. Chen et al., A hybrid directional microvibration energy collection for self-powered
energy cell for self-powered water splitting. Energy Environ. multifunctional systems based on hybridized nanogenerators.
Sci. 6(8), 2429–2434 (2013). https://doi.org/10.1039/C3EE4 ACS Nano 14(3), 3328–3336 (2020). https: //doi.org/10.1021/
1485J acsnano.9b08998
165. L. Jin, B. Zhang, L. Zhang, W. Yang, Nanogenerator as new 177. J.-W. Lee, W. Hwang, Theoretical study of micro/nano rough-
energy technology for self-powered intelligent transporta- ness effect on water-solid triboelectrification with experimen-
tion system. Nano Energy 66, 104086 (2019). https://doi. tal approach. Nano Energy 52, 315–322 (2018). https://doi.
org/10.1016/j.nanoen.2019.104086 org/10.1016/j.nanoen.2018.08.008
166. X. Xia, H. Wang, P. Basset, Y. Zhu, Y. Zi, Inductor-free out- 178. J. Xiong, H. Luo, D. Gao, X. Zhou, P. Cui, G. Thangavel, K.
put multiplier for power promotion and management of tri- Parida, P.S. Lee, Self-restoring, waterproof, tunable micro-
boelectric nanogenerators toward self-powered systems. ACS structural shape memory triboelectric nanogenerator for self-
Appl. Mater. Interfaces 12(5), 5892–5900 (2020). https: //doi. powered water temperature sensor. Nano Energy 61, 584–593
org/10.1021/acsami.9b20060 (2019). https://doi.org/10.1016/j.nanoen.2019.04.089
167. J. Han, X. Meng, L. Lu, Z.L. Wang, C. Sun, Triboelec- 179. Y. Feng, L. Zhang, Y. Zheng, D. Wang, F. Zhou, W. Liu,
tric nanogenerators powered electrodepositing tri-func- Leaves based triboelectric nanogenerator (TENG) and
tional electrocatalysts for water splitting and rechargeable TENG tree for wind energy harvesting. Nano Energy
zinc–air battery: a case of Pt nanoclusters on NiFe-LDH 55, 260–268 (2019). https : //doi.org/10.1016/j.nanoe
nanosheets. Nano Energy 72, 104669 (2020). https://doi. n.2018.10.075
org/10.1016/j.nanoen.2020.104669 180. H. Lin, M. He, Q. Jing, W. Yang, S. Wang et al., Angle-
168. A. Wei, X. Xie, Z. Wen, H. Zheng, H. Lan et al., Triboelec- shaped triboelectric nanogenerator for harvesting environ-
tric nanogenerator driven self-powered photoelectrochemi- mental wind energy. Nano Energy 56, 269–276 (2019). https
cal water splitting based on hematite photoanodes. ACS ://doi.org/10.1016/j.nanoen.2018.11.037
Nano 12(8), 8625–8632 (2018). https://doi.org/10.1021/ 181. K. Han, J. Luo, Y. Feng, Q. Lai, Y. Bai, W. Tang, Z.L. Wang,
acsnano.8b04363 Wind-driven radial-engine-shaped triboelectric nanogenera-
169. S. Shittu, G. Li, Y.G. Akhlaghi, X. Ma, X. Zhao, E. tors for self-powered absorption and degradation of N O x.
Ayodele, Advancements in thermoelectric generators ACS Nano 14(3), 2751–2759 (2020). https: //doi.org/10.1021/
for enhanced hybrid photovoltaic system performance. acsnano.9b08496
Renew. Sustain. Energy Rev. 109, 24–54 (2019). https:// 182. M.T. Rahman, M. Salauddin, P. Maharjan, M.S. Rasel, H.
doi.org/10.1016/j.rser.2019.04.023 Cho, J.Y. Park, Natural wind-driven ultra-compact and highly
170. X. Meng, J. Han, L. Lu, G. Qiu, Z.L. Wang, C. Sun, efficient hybridized nanogenerator for self-sustained wireless
Fe2+-doped layered double (Ni, Fe) hydroxides as efficient environmental monitoring system. Nano Energy 57, 256–268
electrocatalysts for water splitting and self-powered elec- (2019). https://doi.org/10.1016/j.nanoen.2018.12.052
trochemical systems. Small 15(41), 1902551 (2019). https 183. X. Zhao, B. Chen, G. Wei, J.M. Wu, W. Han, Y. Yang, Poly-
://doi.org/10.1002/smll.201902551 imide/graphene nanocomposite foam-based wind-driven

triboelectric nanogenerator for self-powered pressure sen- Catal. B 225, 121–127 (2018). https: //doi.org/10.1016/j.apcat
sor. Adv. Mater. Technol. 4(5), 1800723 (2019). https://doi. b.2017.11.065
org/10.1002/admt.201800723 195. L. Zhao, Y. Qi, L. Song, S. Ning, S. Ouyang, H. Xu, J. Ye,
184. M. Xie, S. Dunn, E.L. Boulbar, C.R. Bowen, Pyroelectric Solar-driven water–gas shift reaction over C uO x/Al 2O 3
energy harvesting for water splitting. Int. J. Hydrogen Energy with 1.1% of light-to-energy storage. Angew. Chem. Int.
42(37), 23437–23445 (2017). https://doi.org/10.1016/j.ijhyd Ed. 58(23), 7708–7712 (2019). https://doi.org/10.1002/
ene.2017.02.086 anie.201902324
185. Y. Zhang, S. Kumar, F. Marken, M. Krasny, E. Roake et al., 196. N. Liu, M. Xu, Y. Yang, S. Zhang, J. Zhang, W. Wang, L.
Pyro-electrolytic water splitting for hydrogen generation. Zheng, S. Hong, M. Wei, A uδ−–Ov–Ti3+ interfacial site: cat-
Nano Energy 58, 183–191 (2019). https://doi.org/10.1016/j. alytic active center toward low-temperature water gas shift
nanoen.2019.01.030 reaction. ACS Catal. 9(4), 2707–2717 (2019). https://doi.
186. J. Schlechtweg, S. Raufeisen, M. Stelter, P. Braeutigam, A org/10.1021/acscatal.8b04913
novel model for pyro-electro-catalytic hydrogen production in 197. S. Xu, S. Chansai, C. Stere, B. Inceesungvorn, A. Goguet
pure water. Phys. Chem. Chem. Phys. 21(41), 23009–23016 et al., Sustaining metal-organic frameworks for water–gas
(2019). https://doi.org/10.1039/c9cp02510c shift catalysis by non-thermal plasma. Nat. Catal. 2(2), 142–
187. Y. Zhang, P.T.T. Phuong, E. Roake, H. Khanbareh, Y. Wang, 148 (2019). https://doi.org/10.1038/s41929-018-0206-2
S. Dunn, C. Bowen, Thermal energy harvesting using pyro- 198. S.C. Ammal, A. Heyden, Understanding the nature and activ-
electric–electrochemical coupling in ferroelectric materials. ity of supported platinum catalysts for the water–gas shift
Joule 4(2), 301–309 (2020). https://doi.org/10.1016/j.joule reaction: from metallic nanoclusters to alkali-stabilized sin-
.2019.12.019 gle-atom cations. ACS Catal. 9(9), 7721–7740 (2019). https
188. T. Ding, L. Zhu, X.-Q. Wang, K.H. Chan, X. Lu, Y. Cheng, ://doi.org/10.1021/acscatal.9b01560
G.W. Ho, Hybrid photothermal pyroelectric and thermogal- 199. M. Xu, S. Yao, D. Rao, Y. Niu, N. Liu et al., Insights into
vanic generator for multisituation low grade heat harvest- interfacial synergistic catalysis over Ni@TiO2−x catalyst
ing. Adv. Energy Mater. 8(33), 1802397 (2018). https://doi. toward water–gas shift reaction. J. Am. Chem. Soc. 140(36),
org/10.1002/aenm.201802397 11241–11251 (2018). https://doi.org/10.1021/jacs.8b03117
189. S. Pandya, J. Wilbur, J. Kim, R. Gao, A. Dasgupta, C. Dames, 200. D.B. Pal, R. Chand, S.N. Upadhyay, P.K. Mishra, Perfor-
L.W. Martin, Pyroelectric energy conversion with large mance of water gas shift reaction catalysts: a review. Renew.
energy and power density in relaxor ferroelectric thin films. Sustain. Energy Rev. 93, 549–565 (2018). https : //doi.
Nat. Mater. 17(5), 432–438 (2018). https://doi.org/10.1038/ org/10.1016/j.rser.2018.05.003
s41563-018-0059-8 201. J.A. Rodriguez, E.R. Remesal, P.J. Ramírez, I. Orozco, Z.
190. J. Harada, Y. Kawamura, Y. Takahashi, Y. Uemura, T. Liu, J. Graciani, S.D. Senanayake, J.F. Sanz, Water–gas shift
Hasegawa, H. Taniguchi, K. Maruyama, Plastic/ferroelec- reaction on K/Cu(111) and Cu/K/TiO2(110) surfaces: alkali
tric crystals with easily switchable polarization: low-voltage promotion of water dissociation and production of H2. ACS
operation, unprecedentedly high pyroelectric performance, Catal. 9(12), 10751–10760 (2019). https://doi.org/10.1021/
and large piezoelectric effect in polycrystalline forms. J. acscatal.9b03922
Am. Chem. Soc. 141(23), 9349–9357 (2019). https://doi. 202. M. Zhu, P. Tian, R. Kurtz, T. Lunkenbein, J. Xu et al.,
org/10.1021/jacs.9b03369 Strong metal-support interactions between copper and iron
191. K. Zhang, Y. Wang, Z.L. Wang, Y. Yang, Standard and fig- oxide during the high-temperature water–gas shift reaction.
ure-of-merit for quantifying the performance of pyroelectric Angew. Chem. Int. Ed. 131(27), 9181–9185 (2019). https://
nanogenerators. Nano Energy 55, 534–540 (2019). https:// doi.org/10.1002/anie.201903298
doi.org/10.1016/j.nanoen.2018.11.020 203. J. Shi, A. Wittstock, C. Mahr, M.M. Murshed, T.M. Gesing,
192. S. Pandya, G.A. Velarde, R. Gao, A.S. Everhardt, J.D. A. Rosenauer, M. Bäumer, Nanoporous gold functionalized
Wilbur et al., Understanding the role of ferroelastic domains with praseodymia–titania mixed oxides as a stable catalyst for
on the pyroelectric and electrocaloric effects in ferroelectric the water–gas shift reaction. Phys. Chem. Chem. Phys. 21(6),
thin films. Adv. Mater. 31(5), 1803312 (2019). https://doi. 3278–3286 (2019). https://doi.org/10.1039/C8CP06040A
org/10.1002/adma.201803312 204. D. Damma, D. Jampaiah, A. Welton, P. Boolchand, A.
193. L. Kuai, S. Liu, S. Cao, Y. Ren, E. Kan et al., Atomically Arvanitis, J. Dong, P.G. Smirniotis, Effect of Nb modification
dispersed Pt/metal oxide mesoporous catalysts from syn- on the structural and catalytic property of Fe/Nb/M (M = Mn
chronous pyrolysis-deposition route for water–gas shift reac- Co, Ni, and Cu) catalyst for high temperature water–gas shift
tion. Chem. Mater. 30(16), 5534–5538 (2018). https://doi. reaction. Catal. Today (2019). https://doi.org/10.1016/j.catto
org/10.1021/acs.chemmater.8b02144 d.2019.02.029
194. L. Pastor-Pérez, V. Belda-Alcázar, C. Marini, M.M. Pastor- 205. X. Cui, H.-Y. Su, R. Chen, L. Yu, J. Dong et al., Room-tem-
Blas, A. Sepúlveda-Escribano, E.V. Ramos-Fernandez, perature electrochemical water–gas shift reaction for high
Effect of cold ar plasma treatment on the catalytic perfor- purity hydrogen production. Nat. Commun. 10(1), 86 (2019).
mance of Pt/CeO2 in water–gas shift reaction (WGS). Appl. https://doi.org/10.1038/s41467-018-07937-w
13

Li2020 Article WaterSplittingFromElectrodeToG

Uploaded by

Copyright:

Available Formats

Li2020 Article WaterSplittingFromElectrodeToG

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Li2020 Article WaterSplittingFromElectrodeToG

Uploaded by

Copyright:

Available Formats

ISSN 2311-6706

Water Splitting: From Electrode to Green Energy

* Hong Liu, [email protected]; Weijia Zhou, [email protected]

ABSTRACT Hydrogen ­(H2) production is a latent feasibility of renewable clean energy.

a large amount of nonrenewable energy and simultaneously produces greenhouse gas

Solar cells device Spiro

Thermoelectric device Photoeletrode device

ting driven by photoelectrode devices, solar cells, thermoelectric devices, triboelectric

nanogenerator, pyroelectric device or electrochemical water–gas shift device, have been

1 Introduction device, TENG and other devices including pyroelectric and

from sunlight in nature for thermoelectric (TE) device can O2

generate power to provide the voltage of water splitting TiO2

nature, which can be captured by triboelectric nanogenerator Thermoelectric device

reduce the input of external energy. Therefore, it is of great 1000 µF

significance to establish a suitable externally driven sys-

tem of water splitting to reduce external consumption and

Triboelectric Electric energy

oped a variety of green energy system for efficient produc-

© The authors https://doi.org/10.1007/s40820-020-00469-3

Co3O4@C@NF 1.0 M KOH 42@10 96@10 56 89 1.40@10 Ha et al. [31]

2.2 Electrolytic Cell [59–64]. In the AWE, the electrolyte is made up of a caustic

© The authors https://doi.org/10.1007/s40820-020-00469-3

negatively polarized cathode

inactive impurity catalyst particle

(a) Zero Gap Cell (b)

© The authors https://doi.org/10.1007/s40820-020-00469-3

(a) (b) (d) PURGE GAS OUTLET

PAIR 1 PAIR 2 PAIR n

(a) PEM electrolysis (b) PEM electrolysis Catalyst coated membrane

PEM electrolysis R&D

© The authors https://doi.org/10.1007/s40820-020-00469-3

Faradaic efficiency (%)

Cell voltage (V)

NaCl NaCl 20 1.0

Cathodic part Anodic part 0 0.5

(a) Hematite (b) (c) e−

TiO2/CH3NH3PbI3/PTAA/Au DSA CIGS Perovskite

(d) (e) Bipolar FTO Substrates

© The authors https://doi.org/10.1007/s40820-020-00469-3

(a) Cell voltage/V (b) (c)

NFO2 OER HER

(d) photocurrent (e) photocurrent

© The authors https://doi.org/10.1007/s40820-020-00469-3

© The authors https://doi.org/10.1007/s40820-020-00469-3

(a) (b) (c)

p-type Si E0(H 2O/O2)

Thermoelectric generator Thermoelectric Photoelectrochemical cell

(d) (e) 1 Hybrid energy cell (f) 0.4

© The authors https://doi.org/10.1007/s40820-020-00469-3

FR4 Copper Kapton Gold

Photocurrent density (mA cm−2)

(a) Self-powered water splitting Gas circulation system Gas chromatograph

Output current (mA)

200 4 3.4705 µL min−1

© The authors https://doi.org/10.1007/s40820-020-00469-3

Polarization (µC cm−2)

Surface charges −20

rational design of electrolytic cell and electrocatalysts. In Total∶ CO + 2OH− → H2 + CO2−

1~6 MPa 0.1 MPa CO32−

H2 production (mmol h−1 gcat−1)

ABSTRACT Hydrogen (H2) production is a latent feasibility of renewable clean energy.

2.2 Electrolytic Cell [59–64]. In the AWE, the electrolyte is made up of a caustic