Nano Energy 80 (2021) 105545

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Nano Energy
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Review

Recent advances in electrocatalysts for neutral and large-current-density

water electrolysis
Yuanlin Xu a, b, Chen Wang a, b, Yunhui Huang a, b, Jing Fu a, b, c, *
a
School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
b
Institute of New Energy for Vehicles, Tongji University, Shanghai 201804, China
c
Shanghai Key Laboratory of Development & Application for Metallic Functional Materials, Shanghai 201804, China

A R T I C L E I N F O A B S T R A C T

Keywords: Hydrogen as a clean energy resource is considered as one of the most promising alternatives to alleviate energy
Electrochemical water splitting crisis and environmental pollution, which induces the urgent requirement for electrochemical water splitting
Neutral pH that contains the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Compared with
Electrocatalysts
alkaline or acidic electrolytes, the water splitting in neutral media is more daunting and less explored, which is
Freestanding electrodes
mainly attributed to the additional challenge in improving the sluggish kinetics of water dissociation in neutral
Hydrogen evolution reaction
Oxygen evolution reaction pH. However, if the neutral water splitting system could be realized, it would bring about the opportunity to
direct splitting of less corrosive saline water that is the most abundant resource, which allows a massive and
sustainable hydrogen fuel production. Here we review recent research in the development of both HER and OER
electrocatalysts that are operated in neutral conditions from the perspective of the reaction mechanisms, rate-
determining steps, and component-structure-activity correlations. Single-atom catalysts as an emerging field
are also highlighted for their high atom utilization efficiency and high activity. In view of large-current-density
operating conditions, three-dimensional freestanding electrodes where catalysts grow directly on the conductive
substrates become the main tendency. In addition, superhydrophilic and superaerophobic electrode surfaces are
summarized with regard to rapid ion diffusions and gas bubbles release, especially under large current densities.
Finally, we address the challenges associated with neutral water electrolysis and future pathways in the hope of
guiding the design of the electrocatalysts and electrode materials to make large-scale hydrogen production easier
and more efficient.

1. Introduction
With the gradual depletion of non-renewable energy sources such as
coal, oil, and natural gas, it is highly urgent to solve this severe hotspot
issue. Presently, hydrogen as one of the energy alternatives has been
placed high hopes [1]. The current total annual worldwide hydrogen
consumption is in the range of 400–500 billion N m3, and studies show
that the share of hydrogen energy in meeting the final energy needs will
be 11% in 2025 and 34% in 2050 [2,3]. This reasonable prediction is
based on the fact that hydrogen fuel has advantages of high calorific
value, nontoxicity, cleanness, and prospective hydrogen economy that
only requires technologies without regard for political accesses and
national boundaries [4]. The challenge is to seek energy-efficient ap­
proaches to generate hydrogen. Compared with other technologies (e.g.,
steam methane reforming, biomass conversion, and coal gasification),
electrochemical water splitting is more attractive since it not only makes
use of water as a natural carrier of hydrogen but also uses electricity for
carbon-free energy sources, truly realizing the benign circular and
environmental-friendly development. Moreover, water electrolysis is
considered as a promising and feasible strategy to promote the effective
transformation of sustainable sources such as solar energy and wind
power, from electric energy to clean hydrogen fuel, which makes con­
tributions in upgrading biomass, fuel cell-powered transportation, and
other fields, achieving efficient energy storage and conversion. Conse­
quently, electrochemical water splitting has become a rapidly emerging
research focus.
In general, water splitting generates high-purity hydrogen and oxy­
gen via two half-reactions, namely, hydrogen evolution reaction (HER)
and oxygen evolution reaction (OER), respectively [5]. Today, only a
small quantity of hydrogen (about 4% of the worldwide hydrogen

* Corresponding author at: School of Materials Science and Engineering, Tongji University, Shanghai 201804, China.
E-mail address: jingfu@tongji.edu.cn (J. Fu).

https://doi.org/10.1016/j.nanoen.2020.105545
Received 15 August 2020; Received in revised form 5 October 2020; Accepted 23 October 2020
Available online 28 October 2020
2211-2855/© 2020 Elsevier Ltd. All rights reserved.
Y. Xu et al.
production) is produced by water electrolysis because of the poor effi­
ciency of both the OER and HER [6]. Although platinum-group metals
are the most effective catalysts for HER whilst benchmark OER catalysts
are IrO2 and RuO2 at present, the scarcity and prohibitively high cost of
these noble metals hamper their wide applications on a large scale [7,8].
To address this bottleneck, from the further perspective of mass
hydrogen production through industrial water splitting, it is of great
importance to explore low-cost and stable electrocatalysts with com­
parable catalytic activity to that of state-of-the-art catalysts for water
splitting especially at large current densities.
Both HER and OER can perform in acidic, basic, and neutral-pH
environments. HER profits from acidic electrolytes as there are suffi­
cient protons (H+) to be adsorbed on the electrode surface to react, while
it is challenging in alkaline or neutral conditions since their kinetics are
slowed by an additional water dissociation step [9,10]. On the contrary,
basic electrolytes are preferred for OER catalysts with a view to the
satisfactory activity and stability since catalysts are quickly deactivated
due to the dissolution of catalyst materials in acidic media [11–13]. This
circumstance lowers the possibility of an overall water splitting system
generating H2 and O2 simultaneously for the reason that it poses a
challenge for the practice application of electrocatalysts in the same
electrolyte, which encourages studies on neutral water electrolysis ur­
gently [14]. Unfortunately, electrocatalysts showing high performance
in neutral medium are rare. If the neutral water splitting system could be
fulfilled, it may open the door to the realization of direct seawater or
saline water splitting without the requirement of desalination for pH
maintenance, which can bring about a large amount of hydrogen fuel
production in a sustainable way [10]. Given these facts, it is thus highly
paramount to develop cheap and efficient electrocatalysts for water
splitting under neutral media so as to meet diverse commercial and in­
dustrial applications of hydrogen production technology in the near
future.
In recent years, several critical review and perspective articles on
HER and OER electrocatalysts for water splitting have been published
[15–26]. These electrocatalysts mentioned mainly include transition-
metal-based catalysts [27], such as alloys [28], carbides [11], oxides
[29], (oxy)hydroxide [30], sulfides [31], selenides [32], nitrides [33],
phosphides [34], and dichalcogenides [35], as well as carbon-based
catalysts [21], such as heteroatom-doped carbon [14,36] and metal-
embedded carbon [37–39]. Reviewing these transition-metal-based
electrocatalyst studies, the electrocatalytic performance can be also
balanced because of their adjustable electronic structure and unique
physical and chemical features. Due to the abundant species of transition
metal group and rich valence state, the combination of different ele­
ments and proportion could create various construction of transition
metal-based materials, for instance 1D (MnO2 nanowires), 2D (MoS2,
MoTe2, NiSe2, and Mxene-group), and 3D (transition metal dichalco­
genides, metal-organic framework, or other porous structure based on
carbonaceous materials as matrix usually) [40,41]. These advantages
provide the synthesized materials with comparable inherent electro­
catalytic activity, but it is not enough for the commercial application. To
further optimize the performance of electrocatalysts, different modifi­
cation strategies have been conducted, such as defects engineering,
heteroatom doping, heterostructure and interface engineering, and
hybrid with excellent conductive materials, thus enhancing the overall
efficiency of water electrocatalysis [41–43]. To sum up, the majority of
these works primarily focus on the material-synthesis-activity correla­
tion of HER/OER catalysts while design strategies for catalysts based on
reaction mechanisms and large-current-density working conditions are
less highlighted, which requires more investigations from the perspec­
tive of large-scale productions.
In this Review, we recapitulate the exciting recent advances of
effective electrocatalysts for water splitting in neutral media showing
comparable or even better performance to the one achievable with
costly noble metal-based catalysts. In view of the reaction mechanisms
and rate-determining steps of HER/OER in neutral conditions, design
2
Nano Energy 80 (2021) 105545
strategies with respect to the composition and structure of electro­
catalysts are discussed. Additionally, the latest researches on advanced
electrodes are outlined, with an especial emphasis on the morphology,
micro/macro architecture, and wettability in consideration of operating
at high current densities. Finally, the challenges and outlook are pro­
vided for guiding the performance-oriented design rules for robust and
durable HER and OER electrocatalysts/electrodes employed under
neutral-pH conditions and large current densities.
2. Design strategies for electrocatalysts in neutral media
Generally, there are two strategies to improve the catalytic activity of
an electrocatalyst: (1) increasing the intrinsic activity of each active site
via polycrystalline, core-shell, alloy structures, etc., or (2) increasing the
number of active sites through increased loadings or regulated struc­
tures of the catalyst to expose more active sites [44]. It should be noted
that these two strategies are typically employed simultaneously to make
the greatest improvements in activities. Since the amount of catalysts
loaded on a given electrode surface is limited due to mass transport,
enhancing the intrinsic activity of catalysts is considered as a more
desirable way [45]. For this reason, design strategies for electrocatalysts
should be based on the reaction mechanisms of HER/OER and the
component-structure-activity relationship of catalysts.
2.1. Hydrogen evolution reaction
HER is a two-electron transfer reaction and it can occur through
Volmer–Heyrovsky or Volmer–Tafel mechanism [46–48].
In an acidic environment:
H+ + e− + ∗→H∗ (Volmer step)
H+ + e− + H∗ →H2 + ∗(Heyrovsky step)
H∗ + H∗ →H2 + 2∗(Tafel step)
In an alkaline environment:
H2 O + e− + ∗→H∗ + OH− (Volmer step)
H2 O + e− + H∗ →H2 + OH− + ∗(Heyrovsky step)
H∗ + H∗ →H2 + 2∗(Tafel step)
where * denotes an active adsorption site on the catalyst surface. HER is
generally recognized as one intermediates’ adsorption-desorption pro­
cess [49]. As we can see, the adsorbed hydrogen (H∗ ) is always involved
despite the exact routes by which the HER occurs in acidic media, and
thus, the free energy of hydrogen adsorption (∆GH*) is widely accepted
to be the descriptor for HER [22]. According to the Sabatier Principle,
only when a good trade-off is reached between the adsorption and
desorption of molecules/atoms on the electrocatalyst surface forming an
appropriate intermediate bond strength, can the catalytic activity be
optimal [50,51]. In this case, the ∆GH* should be close to zero value.
For neutral HER, there are two intermediates (adsorbed H∗ and OH∗ )
and only H2O supplies hydrogen atoms to generate H2 because of the
lack of H+ and relatively low conductivity [52]. Hence, it is reasonable
to conclude that the energy barrier induced by extra water dissociation
is the cause of the slow kinetics [53]. Under this circumstance, elec­
trocatalysts with moderate adsorption energies for OH∗ and H∗ respec­
tively can accelerate the rate-limiting Volmer step of the water splitting
by the synergetic catalysis. This conclusion has been applied by E.H.
Sargent et al. who presented an HER catalyst comprising Ni and CrOx
sites anisotropically doped onto a Cu surface (CrOx/Cu-Ni) [10]. The
combination of Ni sites and CrOx sites that possess the strong hydrogen
binding energy (HBE) and strong OH binding energy, respectively,
promotes the water dissociation, and then Cu sites having the weak HBE
facilitate rapid H–H coupling to produce H2 (Fig. 1a). Density functional
theory (DFT) calculates the reaction barrier of water splitting of the
Y. Xu et al. Nano Energy 80 (2021) 105545

Fig. 1. Design strategies for HER electrocatalysts with regard to reaction mechanisms in neutral media. (a) Anisotropic surface doping of CrOx/Cu-Ni. M1 and M2
represent metal sites. (b) DFT calculations of activation energies at different stages of HER on CrOx/Cu-Ni. Copyright 2019, Nature Energy. (c) Schematic illustration
of the HER mechanism of np-Cu53Ru47. Copyright 2020, ACS Energy Letters. (d) Minimum-energy paths for water dissociation on Ni (111) and N-Ni (111) with
structures for initial (IS), transition (TS), and final (FS) states. Color code: blue, Ni; yellow, N; red, O; white, H. Copyright 2017, Journal of the American Chemical
Society. (e) Minimum-energy paths for water dissociation on FeP and FeP/FeO interfaces. Copyright 2018, Journal of Materials Chemistry A.

Volmer and Tafel steps and reveals the surface configuration of the
CrOx/Cu-Ni structure. As shown in Fig. 1b, Ni doping of Cu contributes
to stabilizing H (state ②) and CrOx on the Ni-doped Cu surface helps
improve the stability of dissociated H2O (state ③). This hybrid catalyst
shows − 0.01 eV (close to zero) of the change in the energy for water
splitting further proving a good catalytic activity. After this work, Wu
et al. prepared a nanoporous (np) Cu53-Ru47 alloy (Fig. 1c), finding that
the incorporation of Ru atoms into the Cu matrix can tune the electronic
structure of the alloy and optimize the adsorption/desorption of in­
termediates H* and OH* on the Ru sites accelerating the water
adsorption and activation [54]. np-Cu53-Ru47 significantly improves the
neutral HER efficiency exhibiting an ultralow Tafel slope of ~ 35 mV per
decade and an overpotential of ~ 41 mV at a current density of
10 mA cm− 2.
In general, the activity of HER electrocatalysts is closely related to
the ability to adsorb H in acidic media. In alkaline or neutral media,
however, the catalytic activity is determined by the adsorption of H2O
[22]. In light of this, it is essential to select the composition of electro­
catalysts and tailor the surface texture of active sites to supply appro­
priate adsorption energies for H2O and H* to expedite the water
dissociation and hydrogen coupling through stepped-up tandem/
sequential reactions. You et al. prepared a nitrogen-modified porous
nickel framework (N-Ni) only applying 64 mV to achieve 10 mA cm− 2 in
neutral electrolytes, in which the surface electron-rich nitrogen atom not
only benefits the initial water adsorption via forming a hydrogen bond
with the electron-deficient H atom but also facilitates the following
water dissociation via H transfer to N (Fig. 1d) [55]. This surface ni­
trogen modification was proved to have the versatility of improving HER
catalytic activities of inexpensive transition metal catalysts (such as
Ni–Fe, Ni–Cu, and Ni–Co) in neutral medium. As for heterostructure
catalysts, Zuo et al. reported a new form of Fe–O–P nanorods composed
of amorphous Fe oxide (FeOx) and nanocrystalline FeP (denoted as
FeOx/FeP) [56]. DFT calculations suggest that in contrast to the pristine
FeP (011) surface, FeO/FeP has an enhanced water adsorption energy
for a thermodynamically optimized water affinity and the interface
oxide effect decreases the ∆GH* of FeP for better hydrogen adsorption,
exhibiting an overall reduced kinetic energy barrier of the minimum-
energy path for water dissociation (Fig. 1e). More interestingly, it was
found that surface Fe sites on FeP or the FeO cluster accelerate the water
dissociation process through forming Fe-hydrides [56,57]. Likewise,
two-dimensional (2D) MoP/MoS2 heterostructure nanosheets grown on
carbon cloth as an efficient neutral HER catalyst has been designed by
Wu et al. [58]. The synergistic effect between MoS2 and MoP impels the
adsorption of H∗ and H2O on the surface.
Considering the scarcity and high cost of precious metals, other than
the development of noble-metal-free electrocatalysts, single-atom cata­
lysts () have recently emerged as a promising class of HER catalysts by
virtue of the reduced amount of precious metals as well as the amelio­
rated catalytic efficiency [59]. In particular, the atomic-level engineer­
ing strategy for electronic structure tuning can effectively manipulate
catalytic properties of catalysts [60]. Low-coordinated metal single
atoms along with the neighboring atoms on the supports often function
as the catalytical active sites, and the charge-transfer effect of SACs
through enhanced metal-support interaction has been proven to
improve the intrinsic activity of active sites [61,62]. Jiang et al. syn­
thesized single-atom Pt decorated nanoporous Co0.85Se catalyst (Pt/np-
Co0.85Se, Fig. 2a) via electrochemical vacancy engineering and atom
embedding strategy, achieving high catalytic performance with a near-
zero onset overpotential, a low Tafel slope of 35 mV per decade, and a
high turnover frequency of 3.93 s− 1 at − 100 mV in neutral media,
which outperforms the commercial Pt/C catalyst and other reported
transition-metal-based compounds [60]. Such improvement is attrib­
uted to the Pt dopant that strongly optimizes the electronic structure of
surrounding Co atoms, resulting in H2O molecules selectively adsorbed
or bound on the Co sites at the early stage. Then, the generated H*
through the Volmer step can be adsorbed on nearby empty Pt sites and

3
Y. Xu et al.
further be converted to H2 via the Tafel step (Fig. 2a). Consequently, the
electronic interactions between atomic-level Pt and np-Co0.85Se can
reduce the water dissociation energy barrier while significantly favor
the adsorption/desorption behavior of H on the catalyst, which syner­
gistically promotes HER activity. After this work, Zhang et al. also made
use of the vacancy engineering that developed an electrochemical
exfoliation process to prepare Mo2TiC2Tx MXene nanosheets with
abundant Mo vacancies that can offer active sites to trap single Pt atoms
(Mo2TiC2Tx-PtSA) and then enhance the catalytic performance (Fig. 2b)
[63]. This single Pt atoms immobilized catalyst exhibits Pt-like catalytic
kinetics toward HER in acidic and neutral PBS solutions, which is
attributed to the positively charged single Pt atoms supported on MXene
providing the optimum adsorption position for H+ with a quite low
adsorption energy of about − 0.08 eV. More importantly, since the
4
Nano Energy 80 (2021) 105545
Fig. 2. SACs for HER in neutral media. (a)
Schematic illustrations of the fabrication pro­
cedure and HER mechanism of Pt/np-Co0.85Se.
Copyright 2019, Nature Communications. (b)
Illustration of the synthesis mechanism for
Mo2TiC2O2-PtSA during the HER process and
the corresponding characteristic images. Copy­
right 2018, Nature Catalysis. (c) SEM image of a
piece of PtSA-NT-NF, TEM image of an NT from
the piece, and atomic-resolution HAADF image
of the NT show Pt atoms (in red). Pt mass ac­
tivities values of PtSA-NT-NF and Pt/C have
been normalized to the Pt loadings and the
contributions of the NTs and NFs have been
deducted. Copyright 2017, Angewandte Chemie
International Edition. (d) Comparison of Tafel
slopes and overpotentials for different
compositions.
specific activity per metal atom usually increases with the decreasing
size of metal particles, SACs can maximize the efficiency of metal atom
use and meanwhile remarkably decrease the amount of metals, which is
particularly significant for supported noble metal catalysts [64]. Moti­
vated by this, Luo et al. synthesized a centimeter-scale and scalable
catalyst termed PtSA-NT-NF comprising single Pt atoms on CoP-based
nanotube (NT) arrays supported by a Ni foam (Fig. 2c) [65]. Strik­
ingly, the catalytic performance of this catalyst with 1.76 wt% Pt
loading is comparable to that of the commercial 20 wt% Pt/C catalyst.
Moreover, by normalizing activities to the Pt loadings, the HER mass
activities of single Pt atoms on PtSA-NT-NF is four times higher than that
of the commercial Pt/C (Fig. 2c). The results highlight the much
contribution of the single Pt atoms to the improved HER performance
with low precious metal loadings. Referred to the above works, Tafel
Y. Xu et al. Nano Energy 80 (2021) 105545

slope and overpotential as two most significant parameters judging the
electrocatalytic performance are summarized for comparison in Fig. 2d
and give a guidance for further research. Overall, as shown in Fig. 2d,
SACs exhibit lower Tafel slops and overpotentials (10 mA cm− 2) relative
to other species, indicating an exceptive application and prospective
direction of materials design as electrocatalysts in HER.
2.2. Oxygen evolution reaction
OER electrocatalysts remain a daunting challenge due to the kinetic
barrier as OER is a complex multistep and energy-uphill reaction that
involves a four-electron process. The four-step-reaction mechanism at
different pH conditions is as followed [66]:
In an acidic environment:
2H2 O + ∗ →OH∗ + H2 O + H+ + e−
OH∗ + H2 O→O∗ + H2 O + H+ + e−
O∗ + H2 O→OOH∗ + H+ + e−
OOH∗ →O2 + ∗ + H+ + e−
In an alkaline environment:
4OH− + ∗ →OH∗ + 3OH− + e−
OH∗ + 3OH− →O∗ + 2OH− +H2 O + e− (6)
O∗ + 2OH− +H2 O→OOH∗ + OH− +H2 O + e− (7)
OOH∗ + OH− +H2 O→O2 + ∗ + 2H2 O + e− (8)
Unlike in the case of the HER, the OER involves multiple in­
termediates (OOH∗ , OH∗ , an⁢ d O∗ ) making the catalytic process more
complicated where catalysts undergo the hydroxide adsorption/water
adsorption and dissociation, O‒H bond breaking, O‒O bond formation,
and O2 desorption on the surface successively. Significantly, the Gibbs
energy change associated with O∗ ⁢ and HOO∗ is the largest, and conse­
quently, the peroxide formation (Eqs. (3) and (7)) is often viewed as the
thermochemically less favorable step [67,68]. Further, it is found that
metal oxide materials obey a linear scaling relation between OOH∗ ⁢
(1) and OH∗ (∆GOOH∗ = ∆GHO∗ + 3.2 ± 0.2eV), and thus, ∆GO∗ − ∆GHO∗ is
usually used as the descriptor for OER catalysts [67]. Simultaneously,
(2) the Sabatier Principle also makes sense here. The too weak bond
strength between the surface of electrocatalysts and oxygen makes in­
(3) termediates formation difficult and then the potential is limited by the
oxidation of HO∗ [20]. In the opposite case of strong oxygen bonding,
(4) the intermediate states and the adsorbed products are quite stable and
then the formation of HOO∗ limits the potential [20].
Based on the design principles aforementioned, in the same way,
(5) regulating and controlling compositions and structures of OER

Fig. 3. Design strategies for OER electrocatalysts with regard to reaction mechanisms in neutral media. (a) Schematic illustration of A-CoS4.6O0.6 PNCs with CoS
dangling bands in the distorted CoS4.6O0.6 octahedral structure as well as the oxygen incorporation into CoSx hosts. Color code: blue Co; yellow S; red O; white H; vac
= vacancy. (b) The theoretical volcano plot containing different CoS2 (001) surface. Copyright 2017, Angewandte Chemie International Edition. (c) Schematic il­
lustrations of Mo-Co9S8@C and DFT calculated free energy diagram of the elementary electrochemical steps. (d) Gibbs free-energy diagrams for four steps of OER on
Co9S8 and Mo-Co9S8@C. Copyright 2020, Advanced Energy Materials. (e) DFT simulation of hydration on simplified Ni–Fe framework surfaces with Mg2+ doping.
Copyright 2020, Advanced Materials.

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Y. Xu et al. Nano Energy 80 (2021) 105545

electrocatalysts to attain desirable bond strength promoting one
elementary reaction or accelerating the sequential catalysis reactions is
conducive to the improvement of OER electrocatalytic activity. For
example, Cai et al. synthesized an oxygen-incorporated amorphous CoSx
porous nanocubes (A-CoS4.6O0.6 PNCs) (Fig. 3a) possessing a higher OER
kinetics than RuO2 [69]. As the theoretical volcano plots shown in
Fig. 3b, A-CoS4.6O0.6 PNCs with both O replacement and S vacancy has a
higher O affinity, which demonstrates that the O replacement and S
vacancy act as the assistance in dramatically strengthening the O∗
adsorption that can promote water oxidation reaction with high activity.
SACs have also been explored as advanced OER electrocatalysts in pH-
neutral environments for the ability to regulate and control adsorption
free energy of intermediates [70]. For instance, Wang et al. prepared a
noble metal-free SAC composed of single-atomic Mo (0.99%) loaded on
Co9S8-supported (Mo-Co9S8@C) (Fig. 3c) realizing a low onset potential
values of 290 mV and also displaying superior overall water splitting
capability with reasonable stability [71]. In comparing with pristine
Co9S8, the synergistic effect between single Mo atoms and Co sites en­
dows the catalyst to have the optimal intermediate adsorption free en­
ergy (Fig. 3d), which results in a lower theoretical overpotential and an
enhanced OER performance. Unfortunately, there are few literatures
available on SACs for neutral OER electrolysis, which deserves more
attention.
Since the reactant concentration of neutral conditions is several or­
ders of magnitude lower than that of alkaline electrolytes, the neutral
OER is particularly hard [72,73]. For this, capturing and dissociating
water molecules (Eq. (1)) at catalysts interface efficiently is able to favor
OER performance in pH-neutral electrolytes. Zhang et al. took a view
that doping using cations like Mg2+ with a high hydration capacity can
potentially favor more water molecule adsorption and enhance the bond
strength between catalysts surface and water molecules [72]. Given this,
the authors inserted four Mg2+ with the small atomic size into one (015)
facet of a prototypical Ni–Fe–OOH framework to synthesize a hydration-
effect-promoting electrocatalyst (Ni–Fe–Mg), exhibiting an over­
potential of 310 mV at 10 mA cm− 2 and outperforming IrO2 by a margin
of 40 mV. The surface OH terminal groups of the Ni–Fe catalyst deter­
mine the interfacial H2O distribution via hydrogen-bonding interactions
in the absence of Mg2+ cations. While the interfacial water molecules are
attracted by the surface added Mg2+ leading to a shorter distance be­
tween O atoms in water and the metal ions (closer water-oxygen-metal
cation distance as red patches shown in Fig. 3e), which encourages the
water molecule adsorption.
Additionally, there is a trade-off between catalytic activity and
chemical stability when designing an OER electrocatalyst. It is worth
noting that the overpotential of OER on the anode is very high generally
showing more than 460 mV at 10 mA cm− 2 under neutral environments,
which exhibits a low energy efficiency and brings about chemical
instability problems [72]. The high potential creates a severe oxidative
condition where catalyst materials will be easily triggered in the irre­
versible oxidation during operation forming of a new oxidative layer,
which leads to changes of active sites and catalyst reconstructions
[20,74]. Then, the inhomogeneous catalytic active sites along with their
complex interactions pose a formidable challenge for fundamental
studies [61]. For example, it is hard to verify the true catalytically active
species of OER for less stable metal oxides, sulfides, nitrides, and
phosphides under oxidizing potentials [61,75]. Furthermore, the cata­
lytic activity and catalytic behavior of a homogeneous catalyst will be
questioned if corresponding oxides form during the OER. To this point,
polyoxometalates (POMs) have recently been proven as one kind of ideal
catalysts functioning in the fast, reversible, and stepwise multielectron-
transfer reactions due to its highest oxidation state of elements that can
offer POMs predominant catalytic performance and unaffected struc­
tures [76]. With that in mind, Yu et al. reported a homogenous Cu-
substituted POM ([(α-SbW9O33)2Cu3(H2O)3]12− ) electrocatalyst
composed of two selfsame Keggin segments that are linked together via
three Cu2+ atoms (Fig. 4a) for OER in the neutral buffer solution [77].
This robust POM-based copper cluster shows a better catalytic activity
and stability compared with that of equal amounts of CuCl2 under the
same reaction conditions. The different electrocatalytic water oxidation
behavior between them was found as CuCl2 would be driven to CuOx

Fig. 4. Design strategies for OER electrocatalysts with regard to chemical stability and electrical properties. (a) Combined polyhedral representation of
[(α-SbW9O33)2Cu3(H2O)3]12− . Color code: copper, yellow; tungsten, blue; antimony, red; oxygen, gray. (b) SEM images and EDX histograms of the surface of an FTO
glass electrode after 2.5 h of catalytic water electrolysis under an applied voltage of 1.2 V vs. Ag/AgCl electrode in a pH = 7.1 Tris-HCl buffer solution, containing
2.0 mM [(α-SbW9O33)2Cu3(H2O)3]12− or 2.0 mM CuCl2. Copyright 2018, Chemical Communications. (c) Schematic illustration of the dual electrical behavior during
the OER process. Copyright 2016, Advanced Materials. (d) HRTEM images of amorphous cobalt oxo-/hydroxide layers on n-Co2P and a-Co2P after a neutral OER
process. Copyright 2017, Nano Letter.

6
Y. Xu et al.
while no heterogeneous species were generated in situ on the surface of
this POM-based catalyst (Fig. 4b), which confirms its homogeneous
character that is profited from the stable structure of POM. Unfortu­
nately, the specific reasons and mechanisms for the absence of hetero­
geneous species are not mentioned in the original paper, which may be
worthy of further study.
Optimizing the electrical properties of electrocatalysts is another
principle that should be paid attention to since OER is a multielectron
reaction. Most semiconducting/insulating transition metal oxides or
hydroxides as widely-used OER catalysts possess a poor conductivity,
which hinders the electron transport inside the catalyst bulk component
and then impedes the catalytic efficiency [73]. In contrast, transition
metal carbides, nitrides, and phosphides may be promising candidates
for water oxidation due to their excellent intrinsic conductivity [78–81].
For instance, Zhang et al. converted Fe–Ni hydroxides into Fe–Ni
phosphides (FeNi–P) for high-performance oxygen evolution under
neutral conditions and indicated that FeNi–P has better electrical con­
ductivity, which could be ascribed to the effect of phosphorization [82].
While considering the electron transport pathway, Xu et al. proposed
that dual electrical behavior regulation on electrocatalysts successfully
actualized an improved electrochemical OER as the schematic shown in
Fig. 4c [78]. The intrinsically metallic property of transition metal
carbides (Ni3C) facilitates electron transport inside the electrocatalyst
bulk component, and meanwhile, the conductive carbon support pro­
motes the charge transport on the catalyst surface, which significantly
enhances the OER catalytic performance when compared with that of
pure Ni3C, NiO, and NiO/C. Though the ideal conductivity can be
ensured, the directly electrochemical activation process in neutral
media forming active species (e.g., metal oxides or hydroxides) on sur­
faces of these catalysts is quite challenging as there are too strong metal-
metal bonds to break and form active species [73]. In terms of this, Xu
et al. demonstrated that in contrast to direct activation in neutral pH, the
previous activation of electrochemical oxidation of metallic precatalysts
in alkaline media can promote the subsequent OER since the harsh
alkaline environment favors the formation of active species on the
catalyst surface [73]. In this case, they selected a-Co2P and n-Co2P as the
catalysts activated in alkali beforehand and the catalyst direct activated
in neutral OER progress, respectively, finding that a-Co2P has a thicker
layer thickness of the cobalt oxo-/hydroxide active species (Fig. 4d). The
catalytic activity of a-Co2P is better than and even twice as much as that
of n-Co2P, showing a greatly decreased overpotential of about 100 mV at
10 mA cm− 2 compared with that of n-Co2P. Although this alkaline
activation method is complex relatively, it provides a way to improve
the generation of active species for transition metal monoxides.
3. Electrodes for water splitting at large current densities
Though the activity of HER/OER electrocatalysts has been signifi­
cantly improved, it is still tricky to effectively assemble catalysts as
electrodes attaining high energy efficiency under long-term (over a time
of thousands of hours) and large-current-density conditions. First,
powdery catalysts generally need to mix with conductive additives such
as carbon materials and then be casted on a current collector using
polymeric binders (e.g., Nafion) forming an electrode [24]. In this way,
there is a weak adhesiveness between catalysts and substrates, which
inevitably increases the resistance, buries active sites, and makes cata­
lysts easily peel off from electrodes during the long-term and high-
current-density electrocatalysis [24,83]. Second, since HER and OER
are both gas-evolution reactions, a great number of gas bubbles gener­
ated on the electrode surface under the practical operating environment
also causes the peeling off of catalysts and large interfacial resistance
that is not availed to the mass transfer [84]. Third, carbon-based ma­
terials generally as catalysts, conductive additives, and supports will
undergo carbon oxidation, etch, and consequent failure of the electrode
structure under a high oxidizing condition [67,85]. Thus, the good
catalytic performance of electrodes reported presently is mostly
7
Nano Energy 80 (2021) 105545
operated at small current densities (e.g., < 20 mA cm− 2), which is still
far from the practical application targets (> 500 mA cm− 2) and difficult
to meet the needs of industrial electrolyzers [24,86,87]. To tackle these
issues, except for the high intrinsic activity, robustness, and low-cost
materials of catalysts, the morphology and architecture of electrodes
also need to be rationally designed so as to meet the requirement of
rapid ion transport and charge transfer capability, corrosion resistance,
and mechanical stability when involving in large current densities and
continuously intensive gas evolution.
One extensively used strategy is to synthesize integrated self-
supported electrodes where catalysts in situ grown on conductive sub­
strates (Fig. 5a) such as carbon-based supports and metal foam/mesh
[84,86–91]. Constructing binder-free and three-dimensional (3D) elec­
trodes can offer advantages of: (1) ideal conductivity due to highly
conductive support materials; (2) massive active sites originated from
the large electrochemical surface-active area; (3) lower contact resis­
tance and accelerated electron transfer since there are strong coupling
effects between catalysts and well conductive supports; and (4) favored
ion transport and bubble diffusion owing to substrates’ open 3D space or
porous structure [92,93]. This strategy has been widely used in alkaline
electrolytes achieving excellent catalytic performance. For instance, Yu
et al. reported a 3D core-shell non-noble metal nitride-based catalyst
consisting of NiFeN nanoparticles (shell) uniformly decorated on NiMoN
nanorods (core) supported on Ni foam (NiMoN@NiFeN), which serves
as an eminently active and durable OER electrode for alkaline seawater
electrolysis [94]. Among this, the interior NiMoN nanorod cores have
good electronic conductivity and afford a large surface area ensuring
numerous active sites. The robust contact between the NiFeN nano­
particles and NiMoN nanorods facilitate the efficient charge transfer
between the catalysts and electrolytes, which can be manifested by the
results from electrochemical impedance spectroscopy (EIS) showing that
the charge-transfer resistances of NiMoN and NiMoN@NiFeN are only
1.7 Ω and 1.0 Ω, respectively (Fig. 5b). There are also a few signs of
progress in the field of neutral water splitting at about 50 mA cm− 2 of
current densities. For example, Li et al. integrated CoO domains with
CoSe2 nanobelts on titanium mesh (denoted as CoO/CoSe2, Fig. 5c) as a
bifunctional electrode for HER and OER where the flexible nanobelts
and their stacking-growth on Ti mesh endow them with 3D porous ar­
chitecture and thus the large active surface area, efficient electron and
mass transport, which triggers excellent electrocatalytic activity and
physical stability [95]. Apart from serving as the support for catalyst
growth, substrates can also play a role in electrocatalysis. In this
contribution, Lu et al. reported manganese doped nickel oxide/nickel
hetero-structured arrays grown on nickel foam skeleton (Mn–NiO–Ni/
NF) that outperforms the Pt/C benchmark [96]. Especially, the nickel
foam offers nickel species that can migrate to and interact with the
deposited Mn-MOF to make the heterostructure (Mn–NiO–Ni) in situ
grow orderly and tightly on the nickel foam, as shown in Fig. 5d. That is,
this unique 3D structure allows the intimate adhesion between the
catalyst and the support to facilitate charge transfer and sustain the
harsh reaction environment, which induces the superior HER activity
and long-term stability.
As aforementioned, the H2/O2 bubble release is a non-negligible
problem that severely limits the ion transfer and stability of electrodes
at long-term large current densities. To prevent the surface accumula­
tion of gas bubbles from blocking catalytic sites and inhibiting the
diffusion of electrolytes, it is expected to design superwetting electrodes
that favor the wettability between catalysts with aqueous electrolytes
via superhydrophilicity and accelerate the departure of bubbles via
superaerophobicity [97,98]. Nevertheless, it should be noted that since
superhydrophilic surfaces are normally superaerophobic inherently due
to the interfacial energy balance, these two design principles are
generally used simultaneously [99,100].
For superhydrophilicity, the liquid contact angle (LCA) of a droplet
on a solid surface should be as low as possible (e.g., less than 10◦ ) with a
high adhesion force of water [98]. First, the effective wetting of a solid
Y. Xu et al. Nano Energy 80 (2021) 105545

Fig. 5. 3D self-supported electrodes for long-

term and large-current-density water splitting.
(a) Schematic illustration of a self-supported
electrode. Copyright 2017, Advanced Mate­
rials. (b) EIS Nyquist plot of different catalysts
tested at a potential of 1.5 V vs. RHE. Copyright
2019, Nature Communications. (c) Schematic
illustration of the synthesis of CoO/CoSe2.
Copyright 2016, Advanced Science. (d) STEM
images of an individual NiO-Ni heterostructure
within MnO-NiO-Ni composites. k and l are
enlarged STEM images of the areas marked in j.
Copyright 2018, Energy & Environmental
Science.

Fig. 6. Superhydrophilic electrodes. (a) Schematic of the synthesis and wettability of NiFe/NiFe:Pi. Copyright 2017, ACS Catalysis. (b) The layer thickness-
dependent wettability of MoS2 films. Copyright 2014, Nano Letters. (c) Schematic illustration of MoS2/Ni3S2 NW-NF. Copyright 2020, Science Bulletin. (d) Sche­
matic illustration of MoS2/Mo2C. (e) LCAs of a 1 M KOH droplet on different surfaces. Copyright 2019, Nature Communications.

8
Y. Xu et al.
surface by a liquid depends on the higher solid-liquid specific surface
energy. Since hydrophilicity (wettability) as an intrinsic surface prop­
erty depends upon the chemical composition, crystallinity, and surface
topography, it is workable to engineer functional electrode surfaces with
appropriate components and special structures, such as rough, hollow,
and hierarchical to attain moderate surface energy [101–103]. From the
point of view of chemical compositions, Li and Zhao synthesized a
porous nanosheet electrocatalyst composed of NiFe hydroxides and NiFe
phosphates (NiFe/NiFe:Pi) grown on carbon fiber paper (CFP) substrates
as a water oxidation electrode with enhanced wettability [104]. Espe­
cially, the well water adsorption originated from the phosphorylation
that significantly improves the surface wettability and then favors the
contact between electrolytes and the electrode surface, as evidenced by
the reduced LCA (Fig. 6a). Moreover, this electrode remains long-term
stable under a large current density of 250 mA cm− 2. However, this
work has not theoretically demonstrated the reason for the improved
hydrophilicity by phosphate groups, which needs further study. More­
over, layer thickness-dependent wettability studies reported by Gaur
et al. and Guo et al. suggested that the surface energy of MoS2 films
increases with the increased number of atomic layers and converges to a
constant value at about six layers due to the changing van der Waals
interlayer interactions in ultrathin films, which presents that the water-
MoS2 LCA decreases with the increase in the number of MoS2 film layers
(thickness) (Fig. 6b) [102,105]. In addition, as low crystalline can
further increase the wettability, Xue et al. reported a novel electrode
containing long and dense MoS2/Ni3S2 co-axial heterostructure nano­
wires on nickel foam (MoS2/Ni3S2 NW-NF) (Fig. 6c) showing super­
hydrophilicity due to the multilayer and low-crystallinity structure of
the outer MoS2 nanosheets [106]. Additionally, based on the fact that
9
Nano Energy 80 (2021) 105545
the superficial roughness at both the micro- and nanoscale not only
supplies a strong capillary force to pump liquid but also reduces inter­
facial adhesion for facilitated gas bubble release, Luo et al. explored the
roles of morphology and surface chemistry in molybdenum disulfide
microspheres modified by molybdenum carbide nanoparticles (Fig. 6d)
[107–109]. The LCAs are 82.3◦ , 53.8◦ , and ~ 0◦ for Pt foil, MoS2, and
MoS2/Mo2C, respectively, showing the best wettability of MoS2/Mo2C
(Fig. 6e), which ensures the good permeability of liquid electrolytes.
Thanks to the enhanced mass transfer, low overpotentials of 227 mV and
220 mV in both acidic and alkaline media, respectively, at a high current
density of 1000 mA cm− 2 are achieved.
For superaerophobicity, the key point is to increase the roughness of
the electrode surface, which is accompanied by the enlarged gas bubble
contact angle (BCA) and reduced bubble adhesion force, making bubbles
release in small sizes [98,110]. In this regard, the morphology of elec­
trodes plays a crucial role. For instance, the flat and platelet morphol­
ogies hamper bubbles to detach from electrode surfaces [111]. In
contrast, vertically aligned nanoarrays (Fig. 7a) can give rise to effective
gas escaping especially when passing high current densities due to the
discontinuous state of the gas-solid-liquid three-phase contact line be­
tween bubbles with electrode surfaces, which contributes to the excep­
tionally low contact region and smaller adhesion force and is similar to
air bubbles at the microstructured surface of a lotus leaf [112–114].
Recently, Liang et al. developed robust NixFe1− x alloy (core)-ultrathin
amorphous oxyhydroxide (shell) one-dimensional (1D) nanowire arrays
(NixFe1− x-AHNAs, Fig. 7b) yielding large current densities of 500 and
1000 mA cm− 2 stably over 120 h at overpotentials of only 248 mV and
258 mV, respectively [115]. Compared to NF and IrO2/NF, this elec­
trode has a smaller average size of the released bubbles and a higher BCA
Fig. 7. Superaerophobic electrodes with nano­
array structures. (a) Schematic illustration of
the evolution behavior of as-formed H2 bubbles
on CoS2 nano-/microwire arrays compared with
CoS2 film. Copyright 2014, Journal of the
American Chemical Society. (b) Schematic il­
lustrations of the NixFe1− x-AHNA nanowire ar­
rays and the size, BCA of released bubbles
during the OER process. Copyright 2020, En­
ergy & Environmental Science. (c) Schematic
illustration of the bubble behavior on the
different electrode surfaces. Copyright 2020,
Journal of Materials Chemistry A. (d) Schematic
illustration of the adhesion behavior for an H2
bubble on blank NF and Ni2P/NF. Copyright
2019, Journal of the American Chemical
Society.
Y. Xu et al.
of 157.3◦ , which verifies the faster re-exposure of catalytic sites to the
surrounding electrolyte and the superaerophobicity of this 1D archi­
tecture, respectively. Guo et al. compared the 1D carbon-nanotube-
coated nickel sulfide foam (NSF/CNT) with the rough surface of NSF
and 2D nickel-iron layered double hydroxide nanosheets (NiFe-LDH) on
Ni foam (Fig. 7c), finding that ultrasmall bubbles (diameter below ~
100 µm) rapidly left the NSF/CNT surface and formed a gas fog in the
process of HER and OER owing to the lowest adhesive force of the 1D
architecture [116]. Yu et al. prepared a Ni2P nanoarrays catalyst on an
NF (denoted as Ni2P/NF) where Ni2P nanosheets are evenly distributed
on Ni2P nanowire, exhibiting a more tremendous potential to release the
in situ as-formed H2 bubbles with superfast speed and prevent bubble
retention compared with bare NF (Fig. 7d) [117]. Apart from these,
there are also other morphologies of electrodes such as pine-shaped
nanoarrays, hierarchical nanostructures, and nanotube arrays, offering
superaerophobic surfaces to actualize the swift bubble detachment
[97,118,119]. A novel hierarchically 3D structured CoOx decorated
carbon foam and carbon nanotube (CoOx@CNTs/P900) was applied as
an OER anode by Pham et al., which is also able to quickly dispose ox­
ygen bubbles [120]. As having a similar behavior of macroporous Ni
foam with pore sizes from 100 to 200 µm that allows efficient bubble
dissipation, porous carbon foam with pore sizes ranging from 50 to
100 µm can also release bubbles rapidly. More importantly, the flexi­
bility of carbon foam when wetting by water allows pores to be
expanded and thus is beneficial for further bubble escaping.
4. Conclusions and outlook
Recent years have witnessed great progress in the development of
advanced electrocatalysts for water splitting. In this review, from a
standpoint of practical applications, we suggest that it is highly imper­
ative to develop electrochemical water splitting in neutral media and at
large current densities. Owing to the low ion concentration, the kinetics
of neutral HER/OER is more sluggish than that of alkaline/acidic con­
ditions. Considering this, we propose that design strategies for electro­
catalysts of both HER and OER achieving exceptional catalytic
performance in neutral electrolytes should base on the binding energy
between reactants (water molecules or reaction intermediates) and
catalyst surfaces. To be specific, it is important to choose the component
and construct the nanostructure of catalysts so as to offer the optimal
adsorption energy toward reactants and thus exhibit an overall reduced
kinetic energy barrier of the minimum-energy path for reactions. Among
them, SACs are presenting a blooming interest due to their unique
single-atom active moieties along with the strong interactions between
substrates and atomic-level atoms, which can tune the electronic
structure of catalysts and thus favor the adsorption/desorption behavior
especially important for water splitting in neutral media. Additionally,
for OER catalysts, there should be an extra concern for the equilibrium
between catalytic activity and conductivity as well as chemical stability
due to its multi-electron reaction property and severe oxidation issue
aroused by high overpotentials, respectively. On one hand, more
attention should be paid to the conductivity of catalyst materials or
supports. To these points, transition metal carbides, nitrides, and
phosphides may be promising alternatives thanks to the desirable con­
ductivity within bulk catalysts. On the other hand, it is necessary to
verify the real active sites of these heterogeneous catalysts since oxides/
hydroxides will in-situ form on the surface by virtue of oxidative con­
ditions. By contrast, using chemically stable homogeneous catalysts that
have a high tolerance against corrosion under a strongly oxidizing
environment may also be an efficient strategy. When taking industrial
large-current-density water splitting into account, more stringent re­
quirements are placed on charge and mass (ions and bubbles) transfers
that are critical factors to consider within electrodes. Specifically, the
gathering of bubbles on the electrode surface is a vital problem that
hinders the ion transfer and impacts the mechanical stability of elec­
trodes. Consequently, an ideal electrode should meet the following
10
Nano Energy 80 (2021) 105545
needs simultaneously: (i) abundant exposed active sites and excellent
conductivity that can actualize the rapid electron transfer; (ii) high
mechanical stability and strong adhesion between catalysts and current
collectors to prevent active phases from peeling off during long-term
electrocatalysis under violent conditions of large current densities
where massive gas bubbles generated on the electrode surface; (iii)
adequate surface contact regions that supply easy access and enough
exposures to electrolytes, which favors swift ion and bubble diffusions.
Given these, establishing 3D self-supported electrodes that can fulfill
these criteria reveals a broader trend. Moreover, the superhydrophilicity
and superaerophobicity of electrode surfaces are additional character­
istics for the effective mass transfer. The superhydrophilicity provides a
large LCA that can enhance the wettability of electrode surfaces, which
facilitates contact with aqueous electrolytes and thus benefits the ion
transfer. To make it possible, the moderate chemical composition, low
crystallinity, and roughness at micro-/nanoscale of the electrode surface
may be essential parameters to focus on. While the superaerophobicity
guarantees a small BCA that can reduce the bubble adhesion force of
electrode surfaces, which endows a quick bubble detachment with small
bubble sizes. The most feasible method is to construct and tune the
morphology and nanostructure of electrodes, such as nanoarrays and
hierarchical architectures, to ensure small bubble adhesion force and
low contact region between bubbles and electrode surfaces.
Despite apparent progress, the implementation of commercial and
industrial neutral water splitting applications is still a long way off.
From the aspect of electrocatalytic systems, some perspectives are listed
as follows:
(1) Reaction mechanisms of neutral water splitting. Although
mechanisms of OER/HER in neutral and near-neutral electrolytes
have been studied earlier, the exact and generally accepted
mechanism is still not explicit, which makes it remain in its in­
fancy. On one hand, the reported volcano plots for HER kinetics
as a function of Metal-H bond energies did not give sufficient
thoughts to solution pH, that is, the volcano plot plotted with
neutral pH in the third axis is eagerly anticipated. On the other
hand, mechanisms of OER may differ with the influence of the
type of electrocatalytic materials, pH of electrolytes used, tem­
perature, and pressure of the cell. Among them, proton coupled
electron transfer (PCET) with the formation of new O-O bonds on
surfaces is a widely accepted mechanism. In this case, the most
effective design principle is to enhance the adsorption energy of
reactants on catalyst surfaces, which is extensively used by many
reported strategies such as, SACs and hydration-effect-promoting
cation doping above-mentioned. However, recently, the non-
concerted proton-electron transfer mechanism indicating that
O2 generated during the OER on some highly covalent oxides can
come from lattice oxygen is proposed by other researches, which
opens a new possibility for designing electrocatalysts using lattice
oxygen redox processes and thus bypassing design limitations of
PCET. Hence, for the further optimization and promotion of
electrocatalysts, the specific reaction mechanisms remain to be
studied and unified in the following works.
(2) Real catalytically species. Though it is generally considered that
oxides/hydroxides in situ formed during reaction are active sites
of OER catalysts, there are also other works demonstrate that the
catalyst itself serves as an active phase as well. For example,
metal chalcogenides, nitrides, and phosphides, in most cases, are
oxidized to metal oxides/hydroxides on the surface or even in
bulk of catalysts under alkaline media, which raises the question
whether the real catalytically species are metal oxides/hydrox­
ides or original compounds. Therefore, the actual catalytic phases
should also be confirmed when designing OER catalysts in neutral
electrolytes with the help of modern structural or spectroscopic
analysis techniques and computational tools. Simultaneously, it is
sorely necessary to investigate how to rationally control and
Y. Xu et al.
understand such in situ oxidation to form effective active sites
while still retaining highly conductive bulk composites.
(3) Ion effects of electrolytes. Apart from catalysts/electrodes, the
ion effect of neutral-pH electrolytes has a significant influence
during an electrolytic process. Other than pure water, there are
numerous kinds of neutral or near-neutral electrolytes including
various buffer and salt solutions such as phosphate buffer saline,
acetate buffer solution, and CO2 saturated NaHCO3 solution.
Furthermore, to avoid financial and energy costs for the desali­
nation of water sources, direct low-grade/impure and saline
water splitting are of great expectation. Under these circum­
stances, it should be noted that both anions and cations in elec­
trolytes make a difference. On one hand, anions should not be
oxidized during water splitting to influence the catalysis. For
instance, special concerns should be placed on the chlorine evo­
lution reaction (ClER) that occurs on anodes due to the existence
of chloride anions in seawater, which strongly competes with the
OER. On the other hand, cations including Ca2+ and Mg2+ may
deposit on cathode surfaces as hydroxides under the reductive
conditions of HER, leading to the blockage of active sites, reduced
accessible surface area, and eventually catalytic deactivation.
Additionally, the reduction and electrodeposition of dissolved
ions e.g., Cu, Cd, Sn, and Pb also have an impact on cathode
surfaces. In contrast, non-innocent elements such as Fe and Se can
facilitate the proton transfer on reactive interfaces. To avoid the
ion effect, first, it is primary to determine a suitable electro­
chemical potential window for water splitting with selected
electrolytes. Second, it is advisable to make sure that both the
electrocatalyst and electrolyte used have the same anion so as to
avoid the in situ generated interface layer that may affect the
catalytic activity. And since a linear scaling relationship exists
between the Cl and O adsorption energies, it is not feasible to
improve the OER selectivity where it dominates over ClER, which
means that NaCl and KCl are not appropriate electrolytes for
neutral water splitting. Third, the developments of both novel
electrocatalysts and protecting layers on catalyst surfaces that are
capable of inherently resisting the corrosion or poisoning caused
by foreign ion depositions are urgently needed for the long-term
stability and catalytic selectivity. Forth, the detailed and sys­
tematic understanding that explains how different salt or metal
ions influence the catalytic performance also calls for greater
urgency, which may be a useful assistance tool for future
research.
(4) Bubble detachment. In order to mitigate the bubble effect and
improve the bubble management to enhance the catalytic per­
formance and reduce the electrical resistance, especially under
large current densities, we put forward the following strategies
and anticipations:
(i) Fine nanostructures of electrodes. For the H2/O2 gas bubble
release of electrodes, except building nanoarrays, there
could be other customized textures and structures on elec­
trode surfaces to promote more efficient diffusion of ions
and escape of gas bubbles. However, now it is still hard to
use traditional chemical fabrication methods to control the
fine structure and size of pores, leading to low availability.
To this point, 3D printing technology is considered as a
promising preparation method to attain an accurate-control
porous architecture of electrodes. Nevertheless, the rela­
tionship between pore sizes/structures and catalytic per­
formance still needs to be worked out.
(ii) Electrolyte modifications. The massive generation and
timely transportation of bubbles trigger considerable Ohmic
losses in a cell. It is validated that some electrochemically
inert and stable additives added in electrolytes can affect the
affinity between electrolytes and electrode surfaces facili­
tating the bubble management. For example, adding
11
Nano Energy 80 (2021) 105545
surfactants can reduce the surface tension, which can
decrease bubbles’ residence time and thus decrease bubbles’
size, accelerating their detachment from electrode surfaces.
Consequently, great research efforts are anticipated to be
focused on moderate additives added in neutral electrolytes
to minimize bubble effects and improve the efficiency of
electrolyzers.
(iii) External fields. Combined electrodes with the applied mag­
netic field, ultrasonic field, supergravity, and microgravity
in water electrolysis can induce the excess convection to
hinder the bubble accumulation and thus further facilitate
the bubble elimination.
(iv) Controlled bubble release. The process of bubble evolution
can be defined as the nucleation, growth, and detachment
from electrodes. Among them, bubble nucleation sites can be
controlled via hydrophobic sites that have reduced bubble
nucleation energy barrier, which can make bubbles directly
nucleate away from electrocatalytic active sites and impede
gas products from aggregating into large bubbles. Thereon,
introducing partially hydrophobic sites as “islands” on the
electrode surface may take into account, which needs to
consider the composite materials of electrodes. In doing so,
the size, number, and detachment sites of bubbles can also
be controlled through tailoring the size, number, and dis­
tribution of “islands”. In a word, it is more targeted and
efficient to design superaerophobic electrode surfaces on the
basis of the theoretical fundamentals of bubble release
behavior underwater.
(5) Bifunctional catalysts in neutral water electrolysis. For practical
overall water splitting, ideal bifunctional electrocatalysts that
cost less and integrate the merits of HER and OER catalysts are
urgently desirable especially under the same neutral media. Co­
balt-, nickel-, and iron-based bifunctional catalysts have been
developed a lot in water splitting in alkaline conditions in recent
years and have achieved considerable progress. However, few
studies have been done on bifunctional catalysts for overall water
splitting in neutral media, which is eager to attract more inves­
tigation for sake of practical use.
(6) pH fluctuations. Deactivation/degradation of the HER catalyst
materials caused by dramatic pH fluctuations is a major issue in
neutral electrolysis. Local pH shifts induced by the consumption
of H+ near electrode surfaces can lead to precipitation of insol­
uble metal hydroxides. Against this backdrop, except for using
buffer solutions, feasible strategies such as the modification of
electrode interfaces and the addition of supporting electrolytes
are required. Additionally, it is testified that stirring has a posi­
tive effect on HER in alkaline solutions showing the slight drop of
overpotential with stirring. This may offer a doable way for
neutral media to reduce the mass-transfer limitation from the
aspect of the set-up. Furthermore, for the accurate measurement
of pH change on the electrode surface, we suggest using pH-
sensing fluorophores as pH indicators to quantitatively image
pH gradients resulting from reductive currents in the diffusion
layer near cathodic electrodes via a laser-canning confocal
microscope.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors acknowledge the support sponsored by the National
Natural Science Foundation of China (52001232), Shanghai Sailing
Y. Xu et al. Nano Energy 80 (2021) 105545

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[100] C. Shi, X. Cui, X. Zhang, P. Tchoukov, Q. Liu, N. Encinas, M. Paven, F. Geyer, Yuanlin Xu received her B.E. degree in polymer materials and
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phosphorylated nife hydroxide by adjusting catalyst wettability, ACS Catal. 7 Chen Wang received his Master degree in School of Materials
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energy and contact angle of water droplets on ultrathin MoS2 films, Phys. Chem. pervision of Prof. Jing Fu at Tongji University, majoring in
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surface chemistry engineering toward pH-universal catalysts for hydrogen Yunhui Huang received his Ph.D. from Peking University in
evolution at high current density, Nat. Commun. 10 (2019) 269, https://doi.org/ 2000. From 2004–2007, he worked with Prof. John Good­
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X. Lei, L. Jiang, Ultrahigh hydrogen evolution performance of under-water University of Science and Technology. He is now the Director
“superaerophobic” MoS2 nanostructured electrodes, Adv. Mater. 26 (2014) of the Institute of New Energy for Vehicles in Tongji University.
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gas evolution reaction electrodes, Mater. Horiz. 2 (2015) 294–298, https://doi. at Donghua University. Her research interest is to understand
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R. Gao, G. Wang, S.-H. Yu, “Superaerophobic” nickel phosphide nanoarray

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