Research Article

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Dual-Doping and Synergism toward High-Performance

Seawater Electrolysis
Jinfa Chang, Guanzhi Wang, Zhenzhong Yang, Boyang Li, Qi Wang, Ruslan Kuliiev,
Nina Orlovskaya, Meng Gu,* Yingge Du, Guofeng Wang,* and Yang Yang*

appealing due to the free and vastly avail-

Hydrogen (H2) production from direct seawater electrolysis is an economi- able seawater reserved on Earth.[3] How-
cally appealing yet fundamentally and technically challenging approach to ever, the most challenging fundamental
harvest clean energy. The current seawater electrolysis technology is signifi- and technical barrier for direct seawater
cantly hindered by the poor stability and low selectivity of the oxygen evolu- electrolysis is the electrochemical compe-
tition between the oxygen evolution reac-
tion reaction (OER) due to the competition with chlorine evolution reaction in
tion (OER) and chlorine evolution reaction
practical application. Herein, iron and phosphor dual-doped nickel selenide (CER) at the anode due to the very close
nanoporous films (Fe,P-NiSe2 NFs) are rationally designed as bifunctional thermodynamic potentials for OER and
catalysts for high-efficiency direct seawater electrolysis. The doping of Fe CER. The equilibrium potential of CER
cation increases the selectivity and Faraday efficiency (FE) of the OER. While and the hypochlorite formation shows pH-
the doping of P anions improves the electronic conductivity and prevents the dependence in alkaline solution, which
competes with OER (Note that the onset
dissolution of selenide by forming a passivation layer containing P–O species. potential to generate hypochlorite is about
The Fe-dopant is identified as the primary active site for the hydrogen evolu- 0.49 V higher than that of OER, for details
tion reaction, and meanwhile, stimulates the adjacent Ni atoms as active see Supporting Information), jeopardizing
centers for the OER. The experimental analyses and theoretical calculations the Faradaic efficiency of OER and elec-
provide an insightful understanding of the roles of dual-dopants in boosting trolyzer cell voltage.[3,4] Besides, the poor
stability of electrode materials further
seawater electrolysis. As a result, a current density of 0.8 A cm−2 is archived
inhibits the continuous hydrogen produc-
at 1.8 V with high OER selectivity and long-term stability for over 200 h, which tion from seawater electrolysis.[5] Besides
surpasses the benchmarking platinum-group-metals-free electrolyzers. the CER and hypochlorite, the biofouling
and trace metal deposition also hurt the
performance of the seawater electrolysis
1. Introduction for long-term operation, which should be well addressed.[6]
Thus, it is crucial to understand the chemistry toward high-effi-
High-purity hydrogen (H2) produced by water electrolysis is a ciency seawater electrolysis and to design cost-effective, stable
promising alternative to traditional fossil fuels because of its platinum-group-metal (PGM)-free catalysts that can deliver
high energy density of 142 MJ kg−1 and zero-emission.[1] Cur- high current density at the low applied voltage for long-term
rently, traditional water electrolyzers using highly purified water application.[4b] However, most research of seawater electrolysis
as feedstock are incompatible with water distribution issues.[2] was tested in the three-electrode reactors,[4a,c,7] which is fun-
Thereupon, direct seawater electrolysis becomes increasingly damentally important to understand the catalytic reactions at

Dr. J. Chang, G. Wang, Prof. Y. Yang B. Li, Prof. G. Wang

NanoScience Technology Center Department of Mechanical Engineering and Materials Science
Department of Materials Science and Engineering University of Pittsburgh
Department of Chemistry Pittsburgh, PA 15261, USA
Renewable Energy and Chemical Transformation Cluster E-mail: guw8@pitt.edu
University of Central Florida Dr. Q. Wang, Prof. M. Gu
Orlando, FL 32826, USA Department of Materials Science and Engineering
E-mail: Yang.Yang@ucf.edu Southern University of Science and Technology
Dr. Z. Yang, Dr. Y. Du Shenzhen 518055, China
Physical and Computational Sciences Directorate E-mail: gum@sustech.edu.cn
Pacific Northwest National Laboratory R. Kuliiev, Prof. N. Orlovskaya
Richland, WA 99352, USA Department of Mechanical and Aerospace Engineering
The ORCID identification number(s) for the author(s) of this article Renewable Energy and Chemical Transformation Cluster
can be found under https://doi.org/10.1002/adma.202101425. University of Central Florida
Orlando, FL 32816, USA
DOI: 10.1002/adma.202101425

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atomic levels but practically still needs more efforts to be trans-
ferred in the device-scale application at low cell voltage and
high current.[8] Additionally, based on the Nernst equation, the
hydrogen evolution reaction (HER) occurs easily in acidic cir-
cumstances while OER prefers to take place in alkaline media,
leading to unbalanced reaction kinetics of HER and OER cata-
lysts in the membrane-based electrolyzers.[9] Moreover, the
strongly acidic or alkaline electrochemical environments used
mostly in the academic research limit the practical application
of water electrolyzers because of the reduced device lifetime
caused by reactor contamination and corrosion.[10] Thereupon,
it is both fundamentally and practically meaningful to design
novel bifunctional catalysts that can deliver balanced HER and
OER activities in mild electrochemical circumstances for sea-
water electrolysis in a low-cost and high-performance manner.
Among the non-PGM bifunctional catalysts, transition metal
selenides (TMSs) are considered as promising HER catalysts
and the pre-catalysts for OER after forming oxidized surfaces
as active species to catalyze water dissociation.[11] However, the
low electrical conductivity and dissolution/degradation of TMSs
challenge their practical applications in water electrolysis.[12]
Even though cation doping is widely employed to enhance the
electrical conductivity of TMSs, the dissolution issue is still
unaddressed.[8a] Recently studies also suggest that transition
metal phosphides (TMPs) are efficient HER catalysts due to the
coexistence of proton-acceptor sites and hydride-acceptor sites
on the material surface, resulting in the facilitated HER through
“ensemble effect.”[13] Meanwhile, the surfaces of TMPs are easy
to be gradually oxidized in an ambient atmosphere, forming an
active P–O phase for OER.[14] On the other hand, the surface
layer containing P–O species also serves as a passivation layer
to effectively prevent TMPs from further dissolution.[15]
We, herein, propose that the aforementioned issues of TMSs
can be addressed by anion and cation dual-doping. Thus, durable
catalysts with a well-balanced bifunctional HER and OER per-
formance can be achieved for the high-performance seawater
electrolyzer. To prove the proposed concept, iron and phos-
phor dual-doped nickel selenide nanoporous films (Fe,P-NiSe2
NFs) were designed and synthesized as model systems. The
rationale for the Fe,P-NiSe2 NFs is that the bond strength of
Se-H (276 kJ mol−1) is weaker than that of P–H (322 kJ mol−1),
leading to a better capability for the selenides to capture the
reactants and accelerate the discharge step.[16] Meanwhile, the
slightly oxidized Fe,P-NiSe2 surface will suppress the dissolu-
tion issue, leading to stable and well-balanced HER and OER
activities toward high-performance seawater electrolysis.[11] The
Fe-doping was used to improve the electrical conductivity and
OER selectivity of Fe,P-NiSe2 NFs by forming high valence
nickel.[17] Experimental results and density functional theory
(DFT) calculation confirmed that the Fe-dopants were the active
sites for HER, while the Ni atoms adjacent to the Fe-dopants
were the catalytic centers for OER. The dual roles of P-dopants
were revealed to increase the electrical conductivity and to pre-
vent the dissolution of selenide by forming a surface passivation
layer containing P–O species. Furthermore, the Fe,P-NiSe2 NFs
were self-supported on carbon cloth, which could be directly
used as bifunctional catalysts in seawater electrolyzer without
interference from the additives.[15a] As a result, the Fe,P-NiSe2
NFs showed outstanding activity, selectivity, and stability toward
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high-performance seawater electrolysis using natural seawater
as a feedstock solution. Industrially required current density of
0.8 A cm−2 was achieved at 1.8 V for over 200 h with an O2 FE
above 92%, which surpasses the state-of-the-art PGM-free water
electrolyzers.
2. Discussion
The dual-doped Fe,P-NiSe2 NFs were anodically converted from
the electrodeposited FeNi alloy films,[18] followed by thermal
treatments using a chemical vapor deposition apparatus (more
experimental details in Supporting Information). To under-
stand the roles of dual-doping effects, control samples prepared
with Fe and P mono-doping (denoted as Fe-NiSe2 and P-NiSe2,
respectively) and the undoped NiSe2 NFs were synthesized.
The quantitative composition analysis by XRF (Figure S1 and
Table S1, Supporting Information) shows that the atom ratios of
Fe: Ni and P: Se are about 1:10 and 1:15, respectively. The incor-
poration of Fe- and P-dopants did not change the primary phase
of NiSe2 as identified by X-ray diffraction (XRD, Figure S2, Sup-
porting Information). While the doping effects on the crystal
structure of NiSe2 were reflected by the slight shift of XRD peaks
to lower angles compared to the undoped NiSe2 because of the
different ionic radius between dopants and host. Fourier trans-
form infrared spectroscopy (Figure S3, Supporting Information)
and Raman spectra (Figure S4, Supporting Information) further
confirmed that Fe and P dual-doping did not significantly affect
the primary phase of NiSe2, without forming any secondary
phase or impurity. The crystal structure of the dual-doped
Fe,P-NiSe2 NFs is schematically illustrated in Figure  1a based
on the above-discussed structural analyses. The morphological
analyses performed by top-view and cross-sectional scanning
electron microscopy (SEM, Figure 1b,c) demonstrate the forma-
tion of a nanoporous structure throughout the entire film in a
total thickness of 5 µm. The nanoporous films are composed of
a thin layer (600 nm) of Fe,P-NiSe2 NFs on the surface as active
materials for catalytic reactions, and the unreacted FeNi alloy
matrix intentionally remained underneath the Fe,P-NiSe2 layer
as conducting support to maintain the structural integrity of the
films (SEM-EDX mapping, Figure S5, Supporting Information).
Further morphological analyses examined by transmission
electron microscopy (TEM, Figure S6, Supporting Informa-
tion) show a layer-by-layer laminated structure of Fe,P-NiSe2
NFs, consistent with SEM observations. Aberration-corrected
annular bright-field scanning transmission electron micro­
scopy image (Figure  1d) and selected area electron diffraction
(inset in Figure  1d) show the well-defined lattice fingerprint
and good crystallization, with a slightly expanded lattice spacing
of 0.32 nm as compared to that of standard NiSe2 (011) plane
(0.31 nm), due to the doping effect.[19] High-resolution high-
angle annular dark-field (HAADF) STEM images (Figure  1e)
taken under the [103] zone axis show the lattice spacing of
0.296 nm corresponding to NiSe2 (101) plane. The enlarged
HAADF-STEM image shown in Figure  1f confirms the crystal
structure of NiSe2. The STEM image (Figure  1g) and the corre-
sponding energy-dispersive X-ray spectroscopy element mapping
images (Figure 1h) prove the coexistence and homogeneous dis-
tribution of Ni, Se, Fe, and P throughout the nanoporous films.
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Figure 1.  Material characterizations of Fe,P-NiSe2 NFs. a) Schematic of the dual-doped structure. b) Top-view and c) cross-sectional SEM images.
d) ABF-STEM image. The inset in (d) is the SAED pattern. e) HAADF-STEM image. f) Enlarged image from (e) and the simulated NiSe2 along [103] zone
axis. g) STEM image and h) the corresponding EDS mapping of Fe,P-NiSe2 NFs. Scale bars: b,c) 1 µm; d,e) 2 nm; f) 1 nm; g,h) 100 nm. The green and
orange spheres in (f) represent Se and Ni, respectively.

X-ray photoelectron spectroscopy (XPS) survey spectrum
(Figure S7, Supporting Information) demonstrates the presence
of Ni, Se, Fe, and P elements in the Fe,P-NiSe2 NFs. The high-
resolution XPS Ni 2p peaks for the Fe,P-NiSe2 NFs (Figure S8a,
Supporting Information) centered at around 853.0 eV/870.5 eV
and 859.0 eV/876.3 eV are assigned to Ni2+and satellite peaks,
respectively.[20] The XPS Se 3d profile (Figure S8b, Supporting
Information) shows the peaks at 54.2 and 55.0 eV ascribed to
the core level bands of Se in NiSe2.[21] Additionally, the fitted
peaks at 56.1 and 57.4 eV are associated with the slightly
oxidized surface.[11,21] The XPS Fe 2p profile (Figure S8c, Sup-
porting Information) shows the oxidized Fe.[22] The XPS P 2p
profile (Figure S8d, Supporting Information) located at 129.2 and
133.3 eV confirms the existence of phosphorus species. The
mono-doped Fe-NiSe2 NFs (Figure S9, Supporting Informa-
tion) have similar Ni, Se, and Fe XPS characteristic peaks to
the dual-doped Fe,P-NiSe2 NFs. However, the Fe,P-NiSe2 NFs
show shift of Ni 2p peaks to lower values than those of P-NiSe2
(Figure S10, Supporting Information) and NiSe2 NFs (Figure S11,
Supporting Information), indicating a strong electronic effect of
Fe,P-NiSe2 NFs. Also, the much higher ratio of P–metal/P–O in
the Fe,P-NiSe2 NFs than that of P-NiSe2 NFs indicates the inhib-
ited surface oxidation by the coupling of Fe and P.
The intrinsic electrochemical HER and OER performance of
the catalysts was firstly examined in Ar-saturated 1.0 m KOH
electrolyte to probe the role of Fe and P dual-doping. The HER
onset potential for the Fe,P-NiSe2 NFs (Figure S12a, Supporting
Information) is 22.6 mV, which is much lower than those of
Fe-NiSe2 NFs (59.2 mV) and P-NiSe2 NFs (98.6 mV), and
close to the Pt/C (0 mV). To reach a high current density of
500 mA cm−2, the overpotentials (η) of 141, 411, and 500 mV
were required for the Fe,P-NiSe2, Fe-NiSe2, and P-NiSe2 NFs,
respectively (Figure  2a). Tafel slopes were estimated to inves-
tigate the rate-determining step (RDS) via the following HER
pathways:[23]
∗ + H2O + e − → OH− + H∗  (1)
H ∗ + H2O + e − → ∗ + OH− + H2  (2)
2H∗ → 2 ∗ + H2  (3)
where * denotes the surface active site. As shown in
Figure S12b,e, Supporting Information, the Fe,P-NiSe2 NFs
have a much smaller Tafel slope (48.9 mV dec−1) than Fe-NiSe2
(94.7 mV dec−1) and P-NiSe2 NFs (146.9 mV dec−1), indicating
the intrinsically favorable HER kinetics. Hence, the RDS
for the Fe,P-NiSe2 NFs is dominated by the Heyrovsky step
(Equation (2), Figure 4e), whereas the Fe-NiSe2 and P-NiSe2 NFs
are controlled by the Volmer step (Equation (3)). The Fe,P-NiSe2
NFs almost represent the best HER catalyst as compared to the
benchmarking catalysts (Figure 2b).
The dual-doped Fe,P-NiSe2 NFs also show much lower OER
overpotentials (Figure S12c,d, Supporting Information, and
Figure 2a) to reach the current densities of 100 and 500 mA cm−2

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Figure 2.  Seawater electrolyzer performance using bifunctional Fe,P-NiSe2 NFs catalysts. a) Comparison of the HER (left) and OER (right) overpoten-
tials required to achieve current densities of 10, 100, and 500 mA cm−2 for: a1) Fe,P-NiSe2 NFs, a2) Fe-NiSe2 NFs, and a3) P-NiSe2 NFs. b,c) Comparison
of Tafel slopes and overpotentials required to achieve current densities of 10 mA cm−2 for HER (b) and 100 mA cm−2 for OER (c) of Fe,P-NiSe2 NFs
with benchmarking works. The performance was tested in 1.0 m KOH with a scan rate of 5 mV s−1 with 90% iR-correction. d) The electrical conductivity
of all samples tested by a four-point probe at room temperature. e) Schematics of the AEM electrolyzers using different electrolyte feeding modes.
I) Sole seawater cathode feeding; II) 0.5 m KOH + seawater cathode feeding; III) Conventional symmetric seawater feeding; and IV) Conventional sym-
metric 0.5 m KOH + seawater feeding. f) The current density of AEM electrolyzer at Ecell of 1.7 and 1.8 V in different seawater feeding modes. g) FE of
O2 using the asymmetric device I (solid) and symmetric device III (dotted) feeding modes using natural seawater as a feedstock solution at different
Ecell. h) Long-term operation test of asymmetric device I and symmetric device III seawater electrolyzers showing high selectivity and stability at 1.8 V.
The FE of O2 is maintained at more than 92% for over the 200 h continuous operation. The error bars in (a), (d), (f), and (g) represent the standard
deviations of at least three independent measurements.

(η of 266 and 317 mV, respectively) than those of the mono-
doped Fe-NiSe2 NFs (η of 280 and 370 mV, respectively) and
P-NiSe2 NFs (η of 299 and 401 mV, respectively). More impor-
tantly, all the catalysts show better OER performance than the
commercial IrO2, which needs η of 359 and 505 mV to reach
current densities of 100 and 500 mA cm−2, respectively. The
Tafel slope (Figure S12e, Supporting Information) of Fe,P-NiSe2
NFs (39.5 mV dec−1) is much lower than those of Fe-NiSe2 NFs
(53.6 mV dec−1) and P-NiSe2 NFs (86.2 mV dec−1), indicating
the facilitated OER kinetics by dual-ion doping (Figure 4e).[24]
∗ + OH− → OH ∗ + e − 
OH ∗ + OH− → O∗ + e − + H2O 
O∗ + OH− → OOH∗ + e −  (6)
OOH∗ + OH− → ∗ + O2 + e − + H2O  (7)
Noticeably, the Fe,P-NiSe2 NFs have a Tafel slope of 39.5 mV
dec−1, indicating that the second-electron transfer process is the
RDS (Figure  4e).[25] Also, the small Tafel slope of Fe,P-NiSe2
NFs suggests that the RDS is at the final step of the multiple-
electron transfer processes, proving an excellent OER activity.
The Fe,P-NiSe2 NFs almost represent the best OER catalysts,
which exhibits the smallest η100 as compared to other represent-
(4) ative works as shown in Figure 2c. For the mono-doped NiSe2
NFs, the much higher Tafel slope indicates that the RDS is con-
(5) trolled by the initial step where the catalyst surface is strongly

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bonded with the hydroxyl group. Faradaic efficiency (FE) was
then evaluated by collecting the evolved gaseous products over
the cathode and anode at 100 mA cm−2 via gas chromatography
(GC). Only H2 and O2 in a volume ratio of 2:1 (FE of 99.5%)
were detected during the water electrolysis (Figure S12f, Sup-
porting Information), further demonstrating the high cata-
lytic activity of Fe-NiSe2 NFs as a bifunctional catalyst for both
HER and OER. Besides, the pristine NiSe2 NFs and FeNi alloy
showed much inferior performance than the Fe,P-NiSe2 NFs
(Figure S13, Supporting Information), confirming the signifi-
cantly boosted intrinsic activity by Fe and P dual-doping.
The electrocatalytic stability tests for the Fe,P-NiSe2 NFs were
performed by chronoamperometry and multi-cycles cyclic vol-
tammetry (Figure S14, Supporting Information). It maintained
stable HER and OER activities for at least 24 h. Moreover, after
5000 cycles of stability test, the LSV polarization curves for
HER and OER show a negligible difference as compared to the
initial curves, further suggesting the outstanding stability of
Fe,P-NiSe2 NFs. The bifunctional HER/OER activities of Fe,P-
NiSe2 NFs were further investigated in a two-electrode system
for overall water splitting (Figure S15, Supporting Information).
Potentials of only 1.73 and 1.81 V were required to deliver a high
current density of 500 mA cm−2 and 1000 mA cm−2, respec-
tively. Electrochemical impedance spectroscopy was used to
probe the reaction kinetics for the catalysts. The Nyquist plots
and the corresponding equivalent circuit show that the charge
transfer resistance (RCT, Table S3, Supporting Information) of
Fe,P-NiSe2 NFs is much smaller than those of mono-doped
(Figure S16, Supporting Information) and undoped catalysts
(Figure S13d, Supporting Information), indicating a greatly
enhanced conductivity, facilitated electron transfer, and thus
improved catalytic activity for both HER and OER due to Fe and
P dual-doping. The double-layer capacitance (CDL, Figure S17,
Supporting Information) of Fe,P-NiSe2, Fe-NiSe2, and P-NiSe2
NFs was estimated to be 1.29, 0.98, and 0.42 mF cm−2, respec-
tively, indicating that the Fe,P-NiSe2 NFs have a much higher
surface area for the catalytic reactions.[26] The unique struc-
ture-dependent catalytic property was investigated by synthe-
sizing and testing Fe,P-NiSe2 nanoplates (NPs, Figure S18a,
Supporting Information), which showed a much worse HER/
OER performance than Fe,P-NiSe2 NFs (Figure S18b,c, Sup-
porting Information), due to the sufficiently exposed surface
active sites in the nanoporous films. To further investigate the
dual-ion doping effects, the electrical conductivity (EC) of all
samples was tested by a four-point probe (Figure 2d). Both Fe-
and P-doping increased the EC of NiSe2 NFs, while the most
optimum EC was achieved by the dual-doped Fe,P-NiSe2 NFs
due to the synergistic electronic interaction.[27] The mechanism
of Fe and P dual-doping was revealed by the DFT calculations
as discussed in the later sections. In a quick summary, both Fe-
and P-doping improved the EC of the catalyst. Besides, the Fe-
doping also served as the active sites for HER and played a vital
role in activating the nearby Ni atoms for OER.[28]
Before testing the performance at the device-scale, we first
evaluated the HER and OER performance of Fe,P-NiSe2 NFs cat-
alyst in pure seawater (collected from the local coast in Florida,
pH ≈8.7, Figure S19, Supporting Information) and 0.5 m KOH +
seawater (Figure S20, Supporting Information). The HER
and OER of Fe,P-NiSe2 NFs tested in 0.5 m KOH + seawater
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electrolytes almost show the same performance as the one
tested in 1.0 m KOH (Figure S20c, Supporting Information),
thus indicating the excellent anti-CER property. While the
worse HER and OER performance was obtained for natural
seawater without KOH due to the low electronic conductivity
(Figure S20d, Supporting Information), which can be compen-
sated by using an alkaline ion exchange membrane. Besides, the
HER and OER activities of Fe,P-NiSe2 NFs were further tested
in Cl−-free 1.0 m phosphate buffer solution (PBS, pH = 8.7). The
Fe,P-NiSe2 NFs need much smaller overpotential than commer-
cial Pt/C and IrO2 to reach a current density of 100 mA cm−2
for HER and OER, respectively (Figure S21, Supporting Infor-
mation). Then, a homemade anion exchange membrane (AEM)
electrolyzer was employed to explore the performance of sea-
water electrolysis (Figure S22, Supporting Information). The
membrane electrode assembly (MEA) consists of Fe,P-NiSe2
NFs as both anode and cathode catalysts (1.2 mg cm−2) separated
by an AEM (Fumasep FAB-PK-130), using the natural (or alka-
line) seawater as feedstock solutions. Recently, Peter Strasser’s
group reported and analyzed six different independent elec-
trolyte feeding ways to avert the limiting applied voltage range
for seawater electrolysis.[8a] Here, the most representative four
different feeding modes were chosen, namely (I–IV) as shown
in Figure  2e, were used to pre-screen the best way to test the
electrolyzer performance. The current densities of 0.305, 0.44,
0.559, and 0.815 A cm−2 were achieved at an electrolysis voltage
of 1.7 V when using (I–IV) feeding modes (Figure  2f and
Figure S23a, Supporting Information), respectively. The current
densities further increased to 0.421, 0.6, 0.769, and 1.144 A cm−2
for (I–IV), respectively, when the voltage was set at 1.8 V.
Noticeably, the seawater electrolysis performance achieved by
the dual-doped Fe,P-NiSe2 NFs far surpasses those of the most
recently reported benchmarking PGM-free catalysts (Table S4,
Supporting Information) and meet the demanding require-
ments (0.4–1 A cm−2) for the practical application in the indus-
tries.[8] Furthermore, the O2 FE at 1.8 V using device III was
examined by gas chromatography (GC, Figure S23b, Supporting
Information) to study the OER selectivity in a complex seawater
circumstance. The O2 FE over 97% (Figure  2g) was detected
when using natural seawater as the cathode feedstock solution
(Figure  2e, device I). If the conventional symmetric seawater
feeding (Figure 2e, device III) was employed, the O2 FE above
92% and a low FE of less than 7% for hypochlorite (ClO−) were
achieved, indicating a high OER selectivity (Figure S24, Sup-
porting Information). Also, the GC result shows that the mole
ratio of H2 and O2 is about 2:1 (Figure S25, Supporting Infor-
mation) using the symmetric seawater feeding (device III) at
the studied potentials, indicating the successfully suppressed
CER. More importantly, the electrolysis efficiency of H2 is above
78.4% at 1.6 V based on the lower heating value (detailed cal-
culation in Supporting Information), which is superior to the
state-of-the-art electrolyzers (Table S4, Supporting Information)
and traditional PGM-based PEM electrolyzers (61.2%),[10a] also
reaching the Department of Energy (DOE) 2020 target (77%).[29]
Furthermore, as compared to the other reported AEM electro-
lyzers using alkaline and purified water (Table S4, Supporting
Information), the seawater electrolyzer presented in this work
using Fe,P-NiSe2 NFs as novel bifunctional catalysts are more
energy-saving and cost-effective. A 200 h continuous and stable
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operation of electrolyzer was further demonstrated using the
asymmetric (device I in Figure  2e) and symmetric (device III
in Figure  2e) models of natural seawater feeding (Figure  2h).
During the continuous testing at a cell voltage (Ecell) of 1.8 V,
well maintained current densities at 0.41 and 0.8 A cm−2 with
the O2 FEO2 above 95% and 92%, respectively, were obtained;
and the ClO− with a very low FE is the main by-product besides
the O2 (Figure S24, Supporting Information). After 200 hours
of continuous electrolysis using device III, the pH of anode
and cathode sides, the specific conductivity of anion-exchange
membrane, and the resistance of MEA have no obvious
change (Figure S26, Supporting Information), indicating the
outstanding durability. This high-performance seawater elec-
trolysis using natural seawater feedstock demonstrated in this
work meets the industrially required current densities for prac-
tical and scalable applications.
The structural integrity of the catalysts after 200 hours of
stability tests using device III (Figure  2e) was examined by
XRD, Raman, XPS, and HR-TEM characterizations. No obvious
change in crystal structure for the post-HER and post-OER
samples was found from XRD (Figure S27a, Supporting Infor-
mation). Raman spectrum (Figure S27b, Supporting Informa-
tion) shows that the post-HER samples almost have the same
characteristic peaks as the as-prepared samples, further veri-
fying the structural stability of Fe,P-NiSe2 at high applied cell
voltages and current densities. While for the post-OER sam-
ples, besides the Tg, Eg, and Ag vibrational modes of Fe,P-NiSe2,
the peaks at 476, 562, and 680 cm−1 assigned to the Ni–O and
Fe–O vibrations were observed because of the slight surface
oxidation under high polarization OER tests.[4c,30] As shown
in Figure S28, Supporting Information, XPS Ni, Se, Fe, and P
peaks of the post-HER samples have no obvious chemical states
change comparing with the as-prepared samples. This result
is consistent with the above-discussed XRD and Raman tests,
proving the excellent stability of the catalyst. For XPS Ni peaks
of the post-OER samples (Figure S29, Supporting Informa-
tion), more Ni2+ was observed due to the slight surface oxida-
tion under high potential OER tests.[11] However, different from
Se disappearance after OER as reported by other researchers,
our samples still have definite Se 3d peaks with a SeOx peak
(Figure S29b, Supporting Information), indicating the stabi-
lized catalyst by alloying with P and forming surface passiva-
tion layer (Figure S29d, Supporting Information).[15a] Thus,
the P-doping not only increased the EC but also prevented the
catalysts from dissolution during electrochemical tests. XPS
O1s peaks of the as-prepared, post-HER, and post-OER samples
were also compared as shown in Figure S30, Supporting Infor-
mation. The adsorbed H2O was found for the as-prepared and
post-HER samples (Figure S30a,b, Supporting Information),
while the lattice oxygen was formed in the post-OER sample
(Figure S30c, Supporting Information), confirming the slight
surface oxidation/passivation of the catalyst.
HR-TEM and EELS mapping were further performed to
probe the valance states and elemental distribution of the
samples (Figure  3). Figure  3a–c shows HR-TEM images of
the as-prepared Fe,P-NiSe2, post-HER, and post-OER sam-
ples. All the samples show very similar morphology and a lat-
tice spacing of 0.32 nm for NiSe2 (011) plane, indicating the
well stabilized structural integrity by Fe and P dual-doping. A
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thin amorphous, oxygen-containing (P–O species) layer was
found on the surface of the post-OER sample (Figure  3c),
indicating the slightly oxidized surface during OER. The
EELS-mapping confirms the homogeneous distribution of Ni
and Fe (Figure  3d–f), as well as, Se and P (Figures S31–S33,
Supporting Information). The intensity ratios of L3/L2 have
a slight increase after OER for both Fe and Ni (Figure  3g–j
and Table S5, Supporting Information), indicating slightly
increased oxidation states of Fe and Ni.[31] Besides, the inten-
sity ratios of Fe L3/L2 at the edges are higher than that of core
regions in all samples, indicating the higher valance state of
the edge than core caused by the surface catalytic reactions.
The Fe and Ni L3/L2 white-line intensity ratios (Figure  3i,j)
show that the valance of +2.6 and +0.76 for Fe and Ni in the
post-HER, respectively. They are quite close to the as-prepared
sample, indicating no obvious change after HER reaction. In
contrast, the valance of +3 and +1.25 was calculated for Fe and
Ni after OER tests, respectively, indicating a slight increase in
the valance states of Fe and Ni. Furthermore, for the post-HER
sample (Figure S32, Supporting Information), no obvious
change in element content and morphology can be found. It
has been reported that the Se in selenide may leach into the
solution during OER,[11] however, the Se in the dual-doped
Fe,P-NiSe2 NFs is unprecedentedly stable (Figures S33 and
S34, Supporting Information) due to the protection from the
surface passivation layer.[15a]
The DFT calculations were performed to predict the reac-
tion pathways on the catalysts using a NiSe2 crystal structure
for HER and OER. For comparison, the catalytic activity on
the surfaces without/with Fe-doping was first studied, namely,
NiSe2 and Fe-NiSe2, as depicted in Figure 4a,b. The predicted
free energy evolution of HER following the Volmer–Heyrovský
mechanism is shown in Figure 4c. Compared to NiSe2 with a
limiting potential of −0.60 V, Fe-NiSe2 was predicted to exhibit
a lower limiting potential of −0.28 V. It is worth noting that
the adsorption site of H* on NiSe2 was surface Ni atoms, in
contrast to the surface Fe atoms on Fe-NiSe2. These results
indicate that the Fe-doping could largely enhance HER activity,
in good agreement with experimental results. Moreover, we
studied specifically the OER activity of a Ni site (Figure 4b), a
Fe site (Figure S35, Supporting Information), and a bridging
Se (Figure S36, Supporting Information) site on the Fe-NiSe2
surface. We predicted that the limiting potential of OER on the
Fe site and bridging Se site were 2.31 and 3.09 V, respectively,
which were much higher than the limiting potential of 1.71 V
on the Ni site (Figure  4c). This result indicates that the Ni
atom on the Fe-NiSe2 surface is the most active site for OER
among all the three possible sites, which is consistent with the
experimental results (Figure S37, Supporting Information). It
is still controversial whether Fe or Ni is the real active site for
the FeNi-based catalysts for OER. Some experimental and DFT
results indicated that Fe is more likely the active site in FeNi-
based catalysts.[32] Much more in-depth studies are needed in
the future to identify the real active sites and the role of Fe
and Ni in the FeNi-based materials for OER. Consistent with
the experimentally observed O-containing layer in Figure  3c,
we further constructed a FeO-NiSe2 (Figure S38, Supporting
Information) surface model to investigate the OER reactivity
of partially oxidized Fe-NiSe2 surface. The limiting potential of
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Figure 3.  TEM and EELS characterization of the catalysts after 200 hours stability tests for device III. a–c) HR-TEM image of Fe,P-NiSe2 NFs with the
as-prepared (a), post-HER (b), and post-OER (c) samples. Scale bars in (a), (b), and (c) are 2 nm, 5 nm, and 5 nm, respectively. d–f) HAADF-STEM
images and the corresponding EELS mappings of the as-prepared (d), post-HER (e), and post-OER (f) samples. g) Fe-L2,3 and h) Ni-L2,3 white-lines
for positions marked in (d), (e), and (f). The calibration curve for i) Fe L3/L2 and j) Ni L3/L2 white-line intensity ratio versus Fe and Ni oxidation state.

OER on the Ni site of the FeO-NiSe2 is predicted to be 1.72 V,
which is very close to the limiting potential of 1.71 V on the
Ni site of unoxidized Fe-NiSe2 (Figure 4d), suggesting that oxi-
dized surface may have little effect on the OER activity of Fe-
NiSe2. In addition, Figure 4d depicts the predicted free energy
evolution of OER on NiSe2 and Fe-NiSe2, the limiting potential
of OER on NiSe2 was predicted to be 1.82 V, whereas Fe-NiSe2
was found to have a lower limiting potential of 1.71 V. These
results suggest that incorporating Fe-dopants could reduce
the overpotential of OER. Moreover, the DFT calculation pre-
dicts that the Ni atom adjacent to Fe atoms on the surface of
Fe-NiSe2 is the active site for OER (Figure  4d), and the RDS

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Figure 4.  DFT simulations. a,b) Atomic structures of the NiSe2 (a) and Fe-NiSe2 (b) surfaces. The gray, orange, and green balls represent Ni, Fe, and
Se atoms, respectively. c,d) Predicted free energy diagrams of HER (c) and OER (d) for NiSe2 and Fe-NiSe2 under the electrode potential of U = 0 and
1.71 V, respectively. e) Illustration for the HER and OER reaction pathways on different catalysts.

of OER is the second electron–proton transfer step, which
is consistent with the result from electrochemical tests. Fur-
thermore, it was found that the density of state increased on
Fermi level by the P-doping (Figure S39, Supporting Informa-
tion), indicating that the P-doping could improve the electrical
conductivity of the catalyst, which in keeping well with the
four-point probe results (Figure 2d). Thus, the Fe and P dual-
doping in the Fe,P-NiSe2 NFs not only resulted in the reduced
adsorption energy and limiting potential, but also increased
the electrical conductivity, all benefit for the activity, stability,
and selectivity toward high-performance seawater electrolysis.
Summarizing the experimental results and DFT calculations,
the HER and OER reaction pathways on the catalysts are
shown in Figure 4e.
3. Conclusion
The dual-doping effects by incorporating Fe- and P-dopants
are proposed and studied to modify the electronic structure
and surface composition of Fe,P-NiSe2, therefore, boosting the
catalyst activity and selectivity toward high-efficiency seawater
electrolysis. The Fe-doping increased the OER activity and the
selectivity. Meanwhile, the P-doping increased the electronic

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www.advancedsciencenews.com
conductivity and improved the stability of the catalyst. As a
result, an industrially required current density of 0.8 A cm−2 was
achieved at 1.8 V for over 200 h in a practical electrolyzer using
natural seawater feedstock, which surpasses the state-of-the-art
electrolyzers and reaches the DOE 2020 target. This work pro-
vides a new avenue for the rational design of non-noble-metal
bifunctional catalysts from the fundamental principles to prac-
tical hydrogen mass production by direct seawater electrolysis.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
J.C., G.W., Z.Y., B.L., and Q.W. contributed equally to this work. Y.Y.
acknowledges the startup support (20080741) from the University of
Central Florida (UCF). J.C. acknowledges the financial support from the
Preeminent Postdoctoral Program (P3) at the UCF. N.O. acknowledges
the financial supports by the NSF MRI 1337758. The XPS test was
supported by the NSF MRI: XPS: ECCS: 1726636, hosted in MCF-AMPAC
facility, MSE, CECS, UCF. A portion of TEM and data analysis was
supported by the U.S. Department of Energy, Office of Science, Office
of Basic Energy Sciences, Early Career Research Program under award
#68278 and performed using EMSL, a DOE User Facility sponsored
by the Office of Biological and Environmental Research and located
at the Pacific Northwest National Laboratory. G.W. acknowledges the
computational resources provided by the University of Pittsburgh Center
for Research Computing as well as the Extreme Science and Engineering
Discovery Environment (XSEDE), which is supported by National
Science Foundation grant number ACI-1053575. M.G. acknowledges
support from Guangdong Innovative and Entrepreneurial Research Team
Program (Grant No. 2019ZT08C044), Shenzhen Science and Technology
Program (KQTD20190929173815000).
Conflict of Interest
The authors declare no conflict of interest.
Author Contributions
Y.Y. led the project. J.C. designed and performed most of the
experiments and analyzed most of the data including material synthesis
and electrochemical tests. G.W. (Guanzhi Wang) performed some of
characterizations. Z.Y., Q.W., Y.D., and M.G. took and analyzed the TEM.
R.K. and N.O. performed the Raman tests. B.L. and G.W. (Guofeng
Wang) performed the DFT calculations. All the authors have discussed
the results and revised the paper together.
Data Availability Statement
Research data are not shared.
Keywords
activity, dual-doping, nickel selenide, seawater electrolysis, stability
Received: February 19, 2021
Revised: April 18, 2021
Published online:
Adv. Mater. 2021, 2101425 2101425  (9 of 10)
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