RESEARCH ARTICLE

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Localizing Tungsten Single Atoms around Tungsten Nitride

Nanoparticles for Efficient Oxygen Reduction
Electrocatalysis in Metal–Air Batteries
Yuanyuan Ma, Yong Yu, Junhui Wang, Jason Lipton, Hui Ning Tan, Lirong Zheng,*
Tong Yang, Zhaolin Liu, Xian Jun Loh, Stephen J. Pennycook, Lei Shen,* Zongkui Kou,*
André D. Taylor,* and John Wang*

1. Introduction
Combining isolated atomic active sites with those in nanoparticles for
synergizing complex multistep catalysis is being actively pursued in the The performance of metal-air batteries is
largely limited by the oxygen reduction re-
design of new electrocatalyst systems. However, these novel systems have
action (ORR) at the air cathodes. Platinum
been rarely studied due to the challenges with synthesis and analysis. Herein, group (PG) metal electrocatalysts have been
a synergistically catalytic performance is demonstrated with a 0.89 V (vs known to possess appealing catalytic ac-
reversible hydrogen electrode) onset potential in the four-step oxygen tivity,[1–3] however, their poor stability and
reduction reaction (ORR) by localizing tungsten single atoms around tungsten cost have driven considerable efforts to de-
velop alternative transition metal-based cat-
nitride nanoparticles confined into nitrogen-doped carbon (W SAs/WNNC).
alysts with excellent catalytic performance.
Through density functional theory calculations, it is shown that each of the We note that both the catalytic activity
active centers in the synergistic entity feature a specific potential-determining and stability are structure-sensitive prop-
step in their respective reaction pathway that can be merged to optimize the erties, which can be optimized by tailor-
intermediate steps involving scaling relations on individual active centers. ing the active material composition, degree
Impressively, the W SAs/WNNC as the air cathode in all-solid-state Zn-air and of dispersion, crystallinity, surface area,
and surface functional groups.[4–6] Previ-
Al-air batteries demonstrate competitive durability and reversibility, despite
ously, it has been shown that moving from
the acknowledged low activity of W-based catalyst toward the ORR. nanoparticles to single atoms can opti-
mize the metal dispersion, which allows

Y. Ma, Y. Yu, J. Wang, H. N. Tan, S. J. Pennycook, J. Wang L. Zheng

Department of Materials Science and Engineering Beijing Synchrotron Radiation Facility Institute of High Energy Physics
Faculty of Engineering Chinese Academy of Sciences
National University of Singapore Beijing 100049, China
Singapore 117574, Singapore E-mail: zhenglr@ihep.ac.cn
E-mail: msewangj@nus.edu.sg T. Yang
Y. Ma, J. Lipton, A. D. Taylor Department of Applied Physics
Department of Chemical and Biomolecular Engineering The Hong Kong Polytechnic University
Tandon School of Engineering Hung Hom, Hong Kong 999077, P. R. China
New York University Z. Liu, X. J. Loh
Brooklyn, NY 11201, USA Institute of Materials Research and Engineering
E-mail: andre.taylor@nyu.edu Agency for Science Technology and Research (A* STAR)
J. Lipton 2 Fusionopolis Way, Innovis 138634, Singapore
Chemical Sciences and Engineering Division L. Shen
Argonne National Laboratory Department of Mechanical Engineering
Lemont, IL 60439, USA National University of Singapore
Singapore 117575, Singapore
E-mail: shenlei@nus.edu.sg
Z. Kou
The ORCID identification number(s) for the author(s) of this article State Key Laboratory of Advanced Technology for Materials Synthesis and
can be found under https://doi.org/10.1002/advs.202105192 Processing
© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH. Wuhan University of Technology
This is an open access article under the terms of the Creative Commons Wuhan 430070, P. R. China
Attribution License, which permits use, distribution and reproduction in E-mail: zongkuikou@whut.edu.cn
any medium, provided the original work is properly cited.
DOI: 10.1002/advs.202105192

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Figure 1. Synthesis routes of W SAs/WNNC and WNNC.
more active species and the exposed surface to participate in cat-
alytic reactions.[7] The catalytic activity can be further enhanced
by modifying the electronic structure, changing the atomic coor-
dination environment, and adjusting the electron confinement
between the metal atoms and the supporting substrate.[8–10]
While nanoparticles and single atoms have been explored for
energy storage and conversion applications,[1,11–14] few studies
have been made that strategically combine them together. We
suggest that combining catalytic active centers with different
potential-determining steps could be an attractive pathway to cir-
cumvent the adsorption-energy scaling relationships on individ-
ual active centers.[15–17] And consequently, this would improve
the overall catalytic performance through step coordination to re-
duce the overall energy barrier in the system. Several recent stud-
ies have successfully demonstrated that the combination of sin-
gle atoms and nanoparticles gives rise to superior catalytic prop-
erties compared to either of the individual counterparts in their
corresponding reaction.[18–21]
Among the various non-PG metal-based materials for ORR,
tungsten (W)-based materials, such as tungsten carbide and ni-
tride nanoparticles, have recently attracted considerable inter-
est, owing to their noble-metal-like d-state density in electronic
structure around the Fermi level, which enables good oxygen
chemisorption.[22,23] However, the oxygen-binding energy of W-
based materials is quite strong, which hinders the competitive
adsorption of OH− species on the W atom surface.[24] Therefore,
applying W-based catalysts for ORR is still a challenge.
Inspired by the strong synergy among the active centers from
more than one catalytic entity, W single atoms coupled with tung-
sten nitride (W3 N4 ) nanoparticle ensembles were investigated in
this work. Here, we examine the catalytic behavior of ensem-
bled single atoms and nanoparticles in ORR and the relationship
between the catalytic activity and the chemical environment. A
unique over-saturation method was first introduced to obtain the
combined entity on a nitrogen-doped carbon substrate through
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entrapping W-based polyoxometalate (W-POM) particles into the
inner cavities of zeolitic imidazolate framework-8 (ZIF-8), fol-
lowed by subsequent pyrolysis. During the formation procedure,
the ZIF-8 was used as a sacrificial template, with the cage frame-
work filled by W-POM. ZIF-8 prevents metal by confining and
separating W-POM species during catalyst synthesis to form the
single atoms. Further, the porous structure of ZIF-8 perseveres
after the pyrolysis process, giving rise to a high surface area of the
resulting catalyst. When evaluated as an ORR catalyst, ensembled
tungsten single atoms on W3 N4 nanocrystals (W SAs/WNNC)
give a high onset potential of 0.89 V versus reversible hydro-
gen electrode (RHE) and a half-wave potential of 0.83 V versus
RHE. The W SAs/WNNC were then directly applied as an air
cathode for both all-solid-state Zn–air and Al–air batteries, which
demonstrate a durable performance (≈13 h for a Zn-air battery
and 250 min for an Al-air battery). The present study represents
a timely addition to the valuable library of synergistic electrocat-
alysts for high-performance metal–air batteries.
2. Results and Discussion
2.1. Preparation of the Catalysts
We illustrate the synthesis routes for W SAs/WNNC and WNNC
in Figure 1. First, ZIF-8 is prepared as the confinement substrate,
as well as the template for the porous structure. The diameter of
ZIF-8’s inner cavity matches well to encase the metal carrier, W-
POM. After the one-step growth of W-POM@ZIF-8, the pyrol-
ysis process renders the conversion of W-POM@ZIF-8 into W
SAs/WNNC. The oversaturation method is refined from one of
our previous spatial confinement methods for single-atom cata-
lyst synthesis.[25] This “one species on one cage” approach allows
enhanced size control of the trapped species, and the spatial con-
finement also restricts the aggregation to obtain high-loading of
single atoms.
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Figure 2. a) XRD curves of all samples. b) SEM images of W SAs/WNNC-5. c) HAADF-STEM image of low-magnification image of W SAs/WNNC-5. d)
STEM-EDS mapping image showing W and N elements. High-resolution STEM image of e) W single atom (red circles) ensembled W3 N4 nanoparticle
and f) a typical W3 N4 nanoparticle.
By adjusting the precursor loading, a tunable combination of
single atoms and nanoparticles can be obtained (Figure 1). In
this work, we modified this method, and prepared a series of W-
POM@ZIF-8 with different amounts of W-POM added, denoted
as W-POM@ZIF-8-x (where x is the amount of W-POM, in mil-
ligrams, in the following values: 5, 10, 20, 40 mg). The subse-
quent pyrolytic products were indicated by W SAs/WNNC-x and
WNNC-x. The pristine ZIF-8 and pyrolyzed products (NC) with-
out W components were also synthesized for comparison pur-
poses.
2.2. Material Characterizations
The precursors and final catalysts were examined for phases us-
ing powder X-ray diffraction (XRD) (Figure S1, Supporting Infor-
mation; Figure 2a). The XRD patterns of the W-POM@ZIF-8 pre-
cursors correspond exactly to that of the standard ZIF-8 without
any presence of other components, which indicates the complete
W-POM entrapment within the crystals of the ZIF-8. Upon cal-
cination, the typical signals of ZIF-8 disappeared, and two peaks
representing the (111) and (200) facets from tungsten nitrides
are clearly observed, confirming the successful conversion of all
samples from W-POM@ZIF-8 precursors to W SAs/WNNC (Fig-
ure 2a). In addition to the XRD phase analysis results, the pres-
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ence of W-POM inside the ZIF-8 crystals was confirmed by mea-
suring the IR absorption peaks. The Fourier-transform infrared
(FTIR) spectrum obtained from the W-POM@ZIF-8-5 is in good
agreement with those of ZIF-8, but no characteristic peak of W-
POM at around 1100 cm−1 is detected, which is taken for the cov-
erage of ZIF-8 (Figure S2, Supporting Information).
We reveal using scanning electron microscopy (SEM) the size
and morphology of the as-synthesized materials (Figures S3 and
S4, Supporting Information). Although the amounts of the en-
trapped W-POM vary, the as-prepared precursors and ZIF-8 have
similar polyhedral structures with a dimension of ≈100 nm.
Taking W SAs/WNNC-5 as an example, the surface of the syn-
thesized polyhedral products become rougher after conversion
(Figure 2b), and a porous nanostructure of W SAs/WNNC-5
is verified using transmission electron microscopy (TEM) and
high-angle annular dark-field scanning transmission electron
microscopy (HAADF-STEM; Figure S5, Supporting Information;
Figure 2c). The corresponding STEM energy-dispersive X-ray
spectroscopy (EDS) mapping image that indicates a uniform el-
emental distribution of W and N (Figure 2d). In fact, the same
morphology transformation has been observed in the catalysts
with higher W-POM loadings, (Figure S6a–c, Supporting Infor-
mation). However, as the W-POM loading increases, so does the
concentration of overlapping nanoparticles. For W SAs/WNNC-
5, the ensembled W single atoms were marked with red circles,
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Figure 3. Electrochemical characterization electrocatalysts. a) CV curves of W SAs/WNNC-5 in O2 -saturated and N2 -saturated 0.1 m KOH. b) Com-
parison of the oxygen reduction polarization curves at a rotating speed of 1600 rpm. c) RRDE voltammograms were recorded for different catalysts in
O2 -saturated 0.1 m KOH at 1600 rpm. d) Electron transfer number at the W SAs/WNNC-5 electrode based on the RRDE result. e) Comparison of current
retention-time response curves in O2 -saturated 0.1 m KOH solution for 16 h. f) Comparison of current retention-time response curves in MeOH solution
for 13 h.

which are clearly found around the neighboring W3 N4 nanoparti-
cles (Figure 2e). Whereas less W single atoms were discovered in
W SAs/WNNC-10 (Figure S6d, Supporting Information), and al-
most no single atoms in WNNC-20 and WNNC-40. As shown by
the Brunauer–Emmett–Teller (BET) analysis, catalysts with sin-
gle atoms have larger specific surface area (Table S1, Support-
ing Information). The atomic resolution STEM-HAADF image
shows that the lattice distance is 0.24 nm, which is consistent
with the (111) plane of W3 N4 (Figure 2f).
We conducted X-ray photoelectron spectroscopy (XPS) to study
the valence states and the electronic interaction of the surface
elements. The full scan spectrum of W SAs/WNNC-5 confirms
the presence of tungsten, nitrogen, and carbon (Figure S7a,
Supporting Information). Regarding the W 4f region, two pro-
nounced peaks, at the respective binding energy of 31.93 and
34.21 eV, could be assigned to tungsten nitrides, correspond-
ing to the core levels of W 4f7/2 and W 4f5/2 (Figure S7b, Sup-
porting Information). From the high-resolution XPS spectra of
N 1s, one peak at 398.7 eV is identified to represent N-W bond-
ing, and the fitted two peaks at 401.3 and 404.5 eV are allocated
to the N-C bonding (Figure S7c, Supporting Information). This
further reinforces the presence of chemical bonding between
W species and the carbon substrate. The W L3-edge X-ray ab-
sorption near edge structure (XANES) spectra of all the samples
are given in Figure S8a,b (Supporting Information). The higher
white line (≈10 209 eV) intensity observed from W SAs/WNNC-
5 and W SAs/WNNC-10 suggests the W inside the single atom
and nanoparticle ensembles has higher average oxidation states
compared with those of WNNC-20 and WNNC-40.[26,27] From the
Fourier transformation (FT) extended X-ray absorption fine struc-
ture (EXAFS) (Figure S8c, Supporting Information), we attribute
the peak located at 2.6 Å to the W–W coordination in tungsten
nitrides, whereas the peak at around 1.95Å suggests the W-N/C
coordination that can be observed in both tungsten single atoms
and tungsten nitrides.[26,27] The X-ray absorption results are in
agreement with the previous conclusion obtained from XPS and
STEM measurements; further proving the successful synthesis
of the binary system.[24]
2.3. Electrochemical Measurements
The cyclic voltammetry (CV) and linear sweep voltammetry (LSV)
curves were collected to analyze the ORR catalytic activities. A
three-electrode workstation with O2 -saturated 0.1 m potassium
hydroxide (KOH) was employed. All potentials were calibrated
to the reversible hydrogen electrode (RHE). Pt/C and NC (ZIF-
8 derived catalyst) were also evaluated as the benchmark and
control samples. The CV curves were obtained after activation,
where the W SAs/WNNC-5 affords a more positive reduction
peak of 0.78 V, which is comparable to Pt/C catalyst, and higher
than that of NC catalyst (Figure 3a; Figure S9, Supporting In-

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Figure 4. Electrochemical performance of the all-solid-state a–c) Zn–air batteries and d–f) Al-air batteries. a) Discharge–charge polarization curve and
power density curves of the solid-state Zn–air batteries. b) Impedance curve of the solid-state Zn−air batteries testing at 1.5 V. c) Cycling stability of the
Zn–air batteries using W SAs/WNNC-5 and Pt/C-Ir/C as the air cathodes. d) Current density and power density of the solid-state Al−air batteries. e)
Impedance curves of the solid-state Zn−air batteries at 1.5 V. f) Discharging stability of the Al–air batteries using W SAs/WNNC-5 and Pt/C as the air
cathodes. Digital images of the assembled solid-state g) Zn–air batteries and h) Al–air batteries with the same voltage measured using a voltammeter
when at flat state and bending state.

formation). Using rotating ring disk electrode (RRDE) measure-
ments, we reveal that W SAs/WNNC-5 has the closest onset po-
tential to Pt/C (0.89 V vs 1.03 V), and its half-wave potential
can reach 0.83 V (Figure 3b). This finding demonstrates a rel-
atively high catalytic activity among the series of W-based cata-
lysts and other ORR catalysts. Refs. [31–36] (Table S2, Supporting
Information).
We show the oxygen reduction polarization curves of other
catalysts collected with different rotating speeds (Figure S10,
Supporting Information). Notably, as the W-POM loading in-
creases, the onset potentials of the derived W SAs/WNNC cat-
alysts demonstrate a negative trend. We suspect that this is a re-
sult of the poor dispersion of W3 N4 nanoparticles and the lack
of W single atoms with increased W-POM loading, as discussed
earlier. Likewise, in comparison with Pt/C and NC catalysts, W
SAs/WNNC-5 gives the smallest ring current density (≈0.023 mA
cm−2 ) for H2 O2 oxidation (Figure 3c), indicating a promising
ORR selectivity. A selective four-electron pathway per oxygen
molecule is determined from the electron transfer number close
to 4 on W SAs/WNNC-5 electrode, thus, a highly effective ORR
process was enabled (Figure 3d). The stability is equally impor-
tant for catalytic performance, and the W SAs/WNNC-5 catalyst
exhibits a similar current retention ratio with that of Pt/C dur-
ing the long-term chronoamperometric tests, as well as a much
better methanol crossover tolerance (Figure 3e,f).
Given the attractive catalytic activity and ORR selectivity, W
SAs/WNNC-5 and the mixture of Pt/C and Ir/C (1:1) were evalu-
ated as the electrode materials for their performance in all-solid-
state Zn–air batteries, and W SAs/WNNC-5 and Pt/C for Al–
air batteries. The charge–discharge polarization curves of Zn–
air battery are shown in Figure 4a. The solid-state Zn–air cell
with W SAs/WNNC-5 cathode delivers the largest power den-
sity of the 11.7 mW cm−2 and a relatively small resistance (Fig-
ure 4b). A stable 12 h cycling plateau with the voltage window
between 1.2 and 2 V is shown in Figure 4c, revealing the supe-
rior stability of the electrode material, which is longer than the
battery with Pt/C–Ir/C electrode (Table S3, Supporting Informa-
tion). Refs. [37–42] For solid-state Al–air battery application, we

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Figure 5. a) Structural model of N-terminal W3 N4 (111) facet, and b) The Gibbs free energy diagram of ORR in the WNs system c)Structural model of
WN4 -G, and d) The Gibbs free energy diagram in the W SAs system.
demonstrate a similar power density and current density as the
Zn–air battery (Figure 4d). This finding indicates a lower resis-
tance in Al–air battery using W SAs/WNNC-5 as the air cath-
ode material (Figure 4e). In addition, we also show a high open
circuit-voltage and long discharge up to 250 min, competitive in
comparison with other reported work (Figure 4f; Table S4, Sup-
porting Information). Refs. [40, 43–47]. A higher discharge volt-
age was also observed compared to those Al-air batteries with the
Pt/C air cathodes. Notably, both metal-air batteries can generate
almost the same open-circuit voltage (OCV) under flat and bent
conditions, indicating good resistance toward mechanical defor-
mation (Figure 4g,h).
2.4. DFT Calculations
In order to understand the underlying mechanism of the im-
proved ORR performance of the ensemble W SAs/WNNC-5, we
performed density-functional theory (DFT) calculations to sim-
ulate both W3 N4 nanoparticles (WNs) and W single atoms (W
SAs) electrocatalytic performance. For the WNs, the (111) facet
(Figure 5a) was considered because the XRD and STEM results
indicate that it is the most exposed surface. As for W SAs, the
WN4 coordination (Figure 5c) was here considered since it has
been reported thermodynamically favorable.[28] The Gibbs free
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energy evolution along the 4-electron ORR pathway was deter-
mined under the computational hydrogen electrode model.[29]
For the WNs, we show that the three-fold N atom is the most
favorable adsorption site (Figure 5a; red circle). As can be seen
from the Gibbs free energy diagram of ORR on the W3 N4 (111)
facet (Figure 5b), the surface N sites can readily activate O2 and
thus facilitate the subsequent hydrogenation step. However, the
last two steps (*O→*OH and *OH→H2 O) are uphill in energy,
with the latter step being the potential-determining step (PDS).
We summarize a more detailed discussion including other poten-
tial structural models considered in this study in Figures S11–S13
(Supporting Information).
With regard to W SAs, our calculations indicate that the most
likely active adsorption site is the neighboring C atom instead of
the central W atom (Figures S14–S20, Supporting Information).
In this case, the O2 activation is found to be the PDS, whereas
all the subsequent steps are downhill in energy at U = 1.23 V
(Figure 5d). Thus, the W SAs and WNs have different PDSs in
ORR and could allow for synergy when active sites are intimately
blended.
We show that the widely observed scaling relation between
*OOH and *OH also holds for both the single WNs and W
SAs system (i.e., G(*OOH) ≈ G(*OH) + 3 eV at U = 0 V) (Fig-
ure 5c,d).[30] Nevertheless, our calculations reveal that they ex-
hibit different capabilities of stabilizing ORR intermediate ad-
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sorbates and thus have different potential-determining steps, as
elaborated in the above discussion. Therefore, when WNs and W
SAs are purposefully integrated, one may expect that they could
complement each other to synergistically catalyse ORR along the
reaction pathway, thereby leading to an improved catalytic perfor-
mance observed in the ensemble W SAs/WNNC-5.
3. Conclusion
In summary, we demonstrate the synergistic combination of the
W single atom and W3 N4 nanoparticle (W SAs/WNNC) as effi-
cient catalysts for ORR, successfully prepared by a new oversat-
uration method to complement the complete cage-confinement
route. With the high catalytic activity for ORR by the synergistic
combination, we also demonstrate a remarkable performance as
metal-air battery cathodes. Our DFT calculations suggest that the
combination of single atoms and nanoparticles provides a signif-
icant opportunity to improve the catalytic performance through
bypassing the scaling relations using simple catalytic materials.
The present work expands the library of synthesized combina-
tions of single atoms and nanoparticles, which represents a novel
material design for wider catalytic applications.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
Y.M., Y.Y., and J.W. contributed equally to this work. This work was sup-
ported by the Singapore Ministry of Education (MOE2018-T2-2-095), re-
search conducted at the National University of Singapore. The authors
acknowledge the funding from Shell.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
Research data are not shared.
Keywords
metal–air batteries, oxygen reduction reaction, single atom catalysts, syn-
ergistic effect, tungsten nitrides
Received: December 3, 2021
Revised: January 20, 2022
Published online:
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