Atomically Dispersed Semimetallic Selenium on Porous Carbon Membrane as an Electrode for Hydrazine Fuel Cells

Article abstract of DOI:10.1002/anie.201907752

Electrochemically functional porous membranes of low cost are appealing in various electrochemical devices used in modern environmental and energy technologies. Herein we describe a scalable strategy to construct electrochemically active, hierarchically porous carbon membranes containing atomically dispersed semi-metallic Se, denoted SeNCM. The isolated Se atoms were stabilized by carbon atoms in the form of a hexatomic ring structure, in which the Se atoms were located at the edges of graphitic domains in SeNCM. This configuration is different from that of previously reported transition/noble metal single atom catalysts. The positively charged Se, enlarged graphitic layers, robust electrochemical nature of SeNCM endow them with excellent catalytic activity that is superior to state-of-the-art commercial Pt/C catalyst. It also has long-term operational stability for hydrazine oxidation reaction in practical hydrazine fuel cell.

Full text of DOI:10.1002/anie.201907752

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
International Edition Chemie
www.angewandte.org
Accepted Article
Title: Atomically Dispersed Semi-Metallic Selenium on Porous Carbon
Membrane as Excellent Electrode for Hydrazine Fuel Cell
Authors: Hong Wang, Tongzhou Wang, Qiang Wang, Yucheng Wang,
Yunli Da, Wu Zhou, Yue Shao, Debao Li, Sihui Zhan, and
Jiayin Yuan
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201907752
Angew. Chem. 10.1002/ange.201907752
Link to VoR: http://dx.doi.org/10.1002/anie.201907752
http://dx.doi.org/10.1002/ange.201907752

Angewandte Chemie International Edition
10.1002/anie.201907752
RESEARCH ARTICLE
Atomically Dispersed Semi-Metallic Selenium on Porous Carbon
Membrane as Excellent Electrode for Hydrazine Fuel Cell
a
b
c
d
d
a
b
Tongzhou Wang , Qiang Wang , Yucheng Wang , Yunli Da , Wu Zhou *, Yue Shao , Debao Li , Sihui
e
c
a
Zhan , Jiayin Yuan , Hong Wang *
Dedicated to 100th Anniversary of Nankai University
Abstract: Electrochemically functional porous membranes of low
cost are appealing in various electrochemical devices used in modern
environmental and energy technologies. Here we describe a scalable
strategy to construct electrochemically active, hierarchically porous
carbon membranes containing atomically dispersed semi-metallic Se,
denoted SeNCM. The isolated Se atoms were stabilized by carbon
atoms in the form of a hexatomic ring structure, in which the Se atoms
were located at the edges of graphitic domains in SeNCM. This
unique atomic configuration is utterly different from that of previously
reported transition/noble metal single atom catalysts. The positively
charged Se, enlarged graphitic layers, robust electrochemical nature
of SeNCM endow them with excellent catalytic activity that is even
superior to state-of-the art commercial Pt/C catalyst, and long-term
operational stability towards hydrazine oxidation reaction in practical
hydrazine fuel cell. This finding will shed light on and initiate the
development and understanding of a family of single semi-metallic
atom heterogenous catalyst for practical applications.
Recently, single-atom catalysts, especially atomically
dispersed metals anchored on conductive nitrogen (N)-doped
carbons (AMCs), have been intensively studied for multifarious
applications10-15 because of their maximized atom utilization,
unusual electronic structure and intriguing properties that differ
from their nanoparticle (NPs) counterpart in terms of i.e. improved
activity and/or selectivity16,17
.
Although there have been progresses in the design of AMCs by
pyrolysis of carefully engineered metal/carbon precursors (i.e.
18
metal-organic-frameworks) , in which metal atoms were
coordinated with N atoms and in the form of typical MN atomic
n
configuration (n represents coordination numbers), controlling the
aggregation of single atoms in carbons during synthesis and in
the later utilization remains challenging, because the high surface
energy makes them easily aggregate into NPs at high pyrolysis
temperature and in complex catalytic reactions, which decrease
19
their activity . Though a very low concentration of the metal
content in precursor could logically mitigate aggregation of single
atoms during pyrolysis, the low content of single atoms in AMC
adversely meet the requirement of practical applications (>1wt%
Introduction
Electrocatalytic hydrazine oxidation reaction (HzOR)1 has
attracted much attention recently because it is not only important
for health and environmental monitoring, but also critical for
hydrazine fuel cells (HzFCs)2,3. Particularly, the latest advance in
1
8
metal content ); Therefore, from a viewpoint of real-life
application, challenges remain in the quest to explore scalable,
efficient synthetic routes to AMC of high single atom content. In
term of a scientific perspective, to correlate the intrinsically
electronic structures of active sites and performance is a
formidable task, since an uncontrollable pyrolysis process makes
alkaline membrane technologies has stimulated intensive studies
4
on HzOR to be used in practical HzFCs . In this context,
it extremely difficult to fabricate MN
configuration throughout carbons.
n
with exactly the same atomic
enormous efforts have been devoted towards developing efficient,
low-cost anode electrocatalysts for HzOR to replace the costly
state-of-the-art platinum (Pt) based nanomaterials5-7, along with
Additionally, intensive studies on single atom catalysts hitherto
1
7
optimizing the electrode fabrication craft8-9
have been focused on transition/noble metals . In this regard, a
very important family of semi-metal elements, i.e. selenium (Se),
has rarely been discussed. It is well-known that Se as redox
center in Se-dependent enzymes is vital to maintain human
.
[
[
a]
b]
Mr. T. Wang, Mr. Y. Shao, Prof. Dr.H. Wang
Key Laboratory of Functional Polymer Materials (Ministry of
Education), Institute of Polymer Chemistry, College of Chemistry,
Nankai University, Tianjin, 300071, P. R. China
E-mail: hongwang1104@nankai.edu.cn
20
health . A structural merit of incorporating semi-metallic atoms is
that they can be easily stabilized by numerous C atoms in form of
covalent bonds rather than a spot of N atoms in N-doped carbons,
creating a well-defined atomic configuration in favor of precisely
correlating their electronic structure and performance.
Herein, we report the first scalable fabrication of semi-metallic
single-atom heterogeneous membrane catalyst that consists of
atomically dispersed Se atoms, which are stabilized by C atoms,
analogous to selenabenzene structure, and anchored on a
hierarchical porous carbon membrane. The membrane is
demonstrated to function as binder-free, high performance
electrocatalyst for HzOR in practical OHzFCs.
Dr. Q. Wang, Dr. B. Hou
State Key Laboratory of Coal Conversion, Institute of Coal
Chemistry, The Chinese Academy of Sciences, Taiyuan, 030001
Shanxi, P. R. China
[
c]
d]
Dr. Y. Wang, Prof. Dr. J. Yuan
Department of Materials and Environmental Chemistry, Stockholm
University, 10691 Stockholm, Sweden.
[
Dr. Y. Da, Prof. W. Zhou
School of Physical Sciences and CAS Centre for Excellence in
Topological Quantum Computation, University of Chinese
Academy of Sciences, Beijing 100190, P. R. China
E-mail: wuzhou@ucas.ac.cn
[f]
Prof. Dr. S. Zhan
Key Laboratory of Pollution Processes and Environmental Criteria
Results and Discussion
(
Ministry of Education), College of Environmental Science and
Engineering, Nankai University, Tianjin 300071, P. R. China
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Angewandte Chemie International Edition
10.1002/anie.201907752
RESEARCH ARTICLE
Figure 1. a-e) Schematic illustration of the preparation process for the SeNCM-x and structural models of the intermediates. f-h) A digital photograph, a cross-
section SEM image and the HRTEM image of SeNCM-1000, respectively. i-l) STEM image and the corresponding elemental mapping.
The electrocatalyst construction was implemented via
a
K as determined by two probe method, which favors fast charge
transport, a mandatory requirement for an efficient electrocatalyst.
Energy-filtered transmission electron microscopy mappings
indicate that C, N, and Se (Figure 1i-l) are uniformly distributed
throughout SeNCM-1000, which is typical for molecular doping of
carbon membrane.
bottom-up method. Figure 1a-e show the synthetic procedure
and structural models of the intermediates and SeNCM. Firstly, a
homogeneous mixture solution of two polymerized ionic liquids,
also termed poly(ionic liquid)s (PILs) in DMF was cast onto a
o
glass plate, dried at 80 C and finally immersed in an aqueous
NH
3
solution to build up the porous PIL membrane (Figure 1b-c.
The atomic structures of SeNCM-x were directly visualized by
atomic-resolution scanning transmission electron microscopy
(STEM) performed in a high-angle annular dark field (HAADF)
mode. The STEM image (Figure 2a) shows a high density of
homogeneously distributed large Se atoms (1.22Å in size)
exclusively in a single-atom state, as represented by bright dots
highlighted with red circles, throughout the SeNCM-1000 matrix.
Moreover, these Se atoms are identified in the thick area of
SeNCM-1000, which revealed that most of them are located at
the edge of graphitic domains. The atomic thickness of graphitic
layer provides an ideal imaging platform for visualizing structural
details at the atomic scale. As shown in Figure 2b, the high-
resolution STEM image obtained in the ultrathin area of SeNCM-
1000 shows four representative Se atoms sitting at the step sites
as the defect sites. The defective nature of SeNCM-x was further
supported by Raman spectrum analysis. The intensity ratio of D
Detail synthesis and characterizations of the PILs and membrane
fabrication procedure were provided in supporting information,
Figure S1-9. Afterwards, in situ pyrolysis21 of the as-prepared PIL
membrane at different temperatures under vacuum leads to the
targeted SeNCM-x, where x indicates the pyrolysis temperature
(
Figure 1d, e). It is worth mentioning the carbon membrane
produced in our laboratory are already several square
centimeters in size (Figure 1f, Figure S10). The fabrication
method is straightforward and readily scaled up to the membrane
in size and quantity.
Figure 1g shows a cross-section scanning electron microscopy
(
SEM) image of SeNCM-1000, in which the three-dimensionally
interconnected porous systems can be clearly observed. High
resolution transmission electron microscopy (HRTEM) image
revealed a well-defined lattice spacing of 0.38 nm for (002) plane
of a graphitic carbon (Figure 1h). This value was larger than that
of common graphite (0.34 nm) because the introduction of large
sized Se bends individual graphitic planes and inevitably enlarges
the interlayer spacing. The sharp X-ray diffraction peaks of
band to G band (I
in the carbons . As shown in Figure S12, the I /I value
D
/I
G
) reflects the degree of structural irregularity
2
2
D
G
increased from 1.09 for SeNCM-800 to 1.16 for SeNCM-1000,
reflecting enhanced structural disorder23 in SeNCM-1000. This
means that SeNCM-1000 may have higher electrocatalytic
activity.
X-ray photoelectron spectroscopy (XPS) revealed that Se
content are 5.90 wt%, 5.06 wt%, and 3.23 wt% in SeNCM-
800/900/1000, respectively, being consistent with inductively
o
o
o
SeNCM-x at 23.3 , 43.8 , and 80.2 are attributed to the (002),
(
(
100), and (110) reflections of a graphitic carbon, respectively
Figure S11). Such a graphitic structure of SeNCM-x endows
them with high conductivity. The conductivity of SeNCM-
-1
800/900/1000 is measured to be 254, 298 and 356 S cm at 298
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Angewandte Chemie International Edition
10.1002/anie.201907752
RESEARCH ARTICLE
2
-1
coupled plasma-atomic emission results. The characteristic Se 3d
signals of SeNCM-x at 56.1 eV is ascribed to the formation the
330, and 450 m g and their total pore volumes are 0.13, 0.15,
3
-1
and 0.17 cm g , respectively (Figure 2f). The observed sharp
uptake of nitrogen at low pressures (P/P < 0.05) provides clear
2
4
Se-C bond
(Figure S13-14). To clearly determine the
0
coordination environment and chemical state of Se atoms in
carbon membrane, X-ray absorption fine structure spectroscopy
evidence for the preservation of micropores (below 2 nm), in
accordance with the pore size distribution curves derived from the
(
XAFS) measurement was performed. As shown in Figure 2c, the
2
N adsorption branch (Figure S18). BET results, taken in
3
Fourier-transformed (FT) k -weighted extended X-ray absorption
fine structure (EXAFS) spectrum shows one main peak at the low
R value of 1.45 Å, in well agreement with the Se-C peak of the
conjunction with SEM imaging, clearly confirm that SeNCM-x is
composed of hierarchical architectures with pores traversing the
micro- to macropore range, which facilitates the charge transfer
and mass diffusion efficiency.
3
,4-propylenedioxyselenophene (ProDOS) reference (the
structure of ProDOS was provided in Figure S15), and no Se−Se
coordination peak at high R value of 2.2 Å was detected. These
results demonstrated that Se is bonded by C and atomically
dispersed throughout the SeNCM-1000. To further clarify the Se
atomic configuration in SeNCM-1000, the EXAFS spectrum was
fitted in the R and k space by the IFEFFIT software (Figure S16-
To demonstrate the practical applications of the newly designed
materials, we directly utilized SeNCM-x as electrodes without the
need for a binder for HzOR. Hydrazine is a very promising liquid
fuel candidate for fuel cells due to its high theoretical
electromotive force (1.56 V), high power density, and
2
5
environmentally benign byproducts (Figure 3a). The cyclic
17). The experimental FT-EXAFS curve of the SeNCM-1000 has
voltammetry (CV) curves of SeNCM-x exhibited obvious oxidation
been perfectly reproduced (Figure 2d). The fitting result gives the
peaks in 1M KOH solution with 100 mM N
2 4
H , but no peaks in the
coordination number of 2, the distance of 1.90 Å, and the disorder
of 0.0058 Å (Table S1). These results suggest that Se atoms
should be located at the edge of SeNCM-1000 in a hexatomic ring
structure (inset in Figure 2d). X-ray absorption near-edge
structure (XANES) shows that the absorption edge position of
SeNCM-1000 is located between that of Se foil and SeO ,
2
suggesting Se atom carries a positive charge and the valence
state of which is between 0 and +4 (Figure 2e).
pure KOH solution (Figure 3b). This reveals that the following
2
-
-
reaction: N
1M KOH with 100 mM N
current densities of SeNCM-800/900/1000 were 0.43/0.40/0.34 V
2
H
4
+ 4OH →N
2
2
+4H O+4e occured over SeNCM-x in
2 4
H
. The onset potentials and peak
-2
(vs. RHE) and 15.6/22.3/30.8 mA cm , respectively. Notably,
SeNCM-1000 has the lowest onset potential and largest peak
current density, demonstrating its highest reactivity towards
HzOR. It is noted that SeNCM-1000 in fact is, to our knowledge,
one of the best electrocatalysts reported so far for HzOR. (Table
S2). The operating stability of HzOR catalysts is essential to their
application. We examined the electrochemical stability of
SeNCM-1000 by both chronoamperometry and cyclic
voltammetry (CV) cycling in 100 mM hydrazine, as shown in
Figure S19-21, no appreciable decrease in current is observed in
this time interval.
In control experiments, it is demonstrated that commercial
nanostructured Se powder (SEM and XRD characterizations were
provided in Figure S22) has no electroactivity for HzOR; N-doped
porous carbon membrane without Se doping (NCM-1000,
structural characterizations were provided in Figure S23-24) has
negligible HzOR activity, which reflected by a very high onset
peak potential (0.6 V vs RHE) and low peak current intensity (5.6
-2
mA cm ). The electrochemical active surface area (ECSA) of
SeNCM-1000 was determined to be 1175 cm2 by double layer
capacitance method25 (Figure S25), which is two orders of
2
magnitudes higher than that of NCM-1000 (57.5 cm ). This
investigation suggests that the existence of atomically dispersed
Se could dramatically enhance the ECSA of SeNCM-1000
thereby exhibiting outstanding catalytic activity toward HzOR.
To deeply understand the HzOR process on SeNCM-1000, the
effects of scan rate () and hydrazine concentration on the
voltammetric waves were systemically investigated (Figure 3c).
) varies linearly with 1 , revealing that
/2
The peak current density (j
the HzOR on SeNCM-1000 is
P
Figure 2. a, b) STEM images of the SeNCM-1000. c) Se K-edge Fourier
transformed EXAFS spectra in the R space of the SeNCM-1000 compared with
the other two references. d) Fourier transformed EXAFS spectrum of SeNCM-
a
diffusion-controlled
electrochemical process (Figure 3d). Furthermore, the linear
1
000 and the corresponding simulation curve, inset is a model structure of
SeNCM-1000. e) Se K-edge XANES of the SeNCM-1000, Se foil and SeO as
the references. f) N absorption-desorption isotherms of SeNCM-x.
dependence of peak current density on hydrazine concentration
2
(
Figure 3e, f) and only an oxidation peak is observed during the
2
CV curves, suggesting that the hydrazine oxidation is irreversible.
To evaluate the possible structural changes of catalyst, we
performed XPS analysis on the SeNCM-1000 before and after
1000 cycles of electrolysis in 100 mM hydrazine. As shown in
The specific surface area is critical for optimizing the activity of
heterogeneous catalysts. The Brunauer-Emmett-Teller (BET)
surface area of the SeNCM-800/900/1000 is measured to be 258,
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Angewandte Chemie International Edition
10.1002/anie.201907752
RESEARCH ARTICLE
3
0
Figure S26-27, the quantity and valence state of N and Se
species of them are quite similar, which is indicative of its
excellent electrochemical stability.
consecutive dehydro-generation steps on Se atom sites : N
2 4
H
→N →N →N H→N (Figure 4). Further experiments are
needed to unveil the detailed mechanism of the HzOR by
SeNCM-x.
2
H
3
2
H
2
2
2
Figure 4. Proposed mechanism of the HzOR on SeNCM-x in 1 M KOH aqueous
solution.
Considering SeNCM-1000 has the highest activity toward
HzOR among all the samples studied in this work, we employed
SeNCM-1000 as anode for fabricating OHzFCs (Figure 5a). For
comparison, 20% Pt/C was also integrated as anode in OHzFCs.
Note that 20% Pt/C was employed as cathode in all studied
OHzFCs in this work using standard procedure in this field for
oxygen reduction reaction and the electrolyte is KOH-doped
polybenzimidazole membrane, unless stated. The performance
testing showed that the open-circuit potential, maximum current
Figure 3. a) Schematic illustration of the SeNCM-x structure and applied for
HzOR. b) CV curves of SeNCM-x, Se powder and NCM-1000 for HzOR (100
mM N
2
H
4
, 1 M KOH, scan rate 5 mV/s). c) CV curves of SeNCM-1000 in 1 M
KOH with 100 mM N
s ). d) Plot of peak current density in relation to the square root of scan rate. e)
CV curves of SeNCM-1000 in different concentrations of hydrazine (10, 20, 40,
2
H
4
at different scan rates (5，10，15，20，40，100 mV
density and power density of SeNCM-1000-OHzFC were 0.91 V,
-
1
-2
6
05.3 mA cm-2 and 182.2 mW cm , respectively (Figure 5b).
-
1
60, 80, 100 mM) in 1M KOH at a scan rate of 100 mV s . f) Plot of peak current
These performance metrics are comparable or even superior to
density with respect to the concentration of hydrazine.
-2
-2
that of Pt/C-OHzFC (0.92 V, 605.4 mA cm and 170.9 mW cm ),
and among the best performances reported so far for OHzFC
To probe the catalytic kinetics of the HzOR on SeNCM-1000,
electrochemical impedance spectroscopy measurement was
conducted under different overpotentials. The series resistance
(
Table S3). Additionally, stability testing showed almost no decay
of SeNCM-1000/HzFC after continuous operations for 6 h (Figure
c), confirming that SeNCM-1000-OHzFC is stable under
5
(
R
s
), pore resistance (R
the HzOR on SeNCM-1000 were fitted by Nyquist plots. As shown
in Figure S28, the overpotential-independent behavior of R (ca.
.55 Ω cm ) for the HzOR indicates the robust nature of the
p
), and charge-transfer resistance (Rct) of
operating conditions. These results suggest promising usability of
SeNCM-1000 for OHzFC.
p
-2
1
hierarchical pore structure of the SeNCM-1000, and these
structures also serve as efficient channels for mass transport to
access the exposed active sites.
Chemically, the outermost orbitals of Se are apparently
overlapped with C atoms, which could introduce the positively
charge characteristics on the Se atoms, being consistent with our
XAFS result. Previous works have demonstrated positively
charged species in heteroatom doped carbons are active
26-27
centers
, in this case, Se atoms. Additionally, the incorporation
of larger atomic radius of Se atom could enlarge graphitic
interlayer spacing and lead to structural strains and defects at the
graphitic edges28, 29, which is in favor of promoting the mass
transportation efficiency in the graphitic layers and exposing
numerous active sites for the HzOR. Based these analyses, the
superior catalytic activity of SeNCM-1000 could mainly be
attributed to the positively charged Se sites and the enlarged
graphitic layer spacing, and the HzOR process may involve four
Figure 5. a) Schematic diagram of OHzFC. b) Polarization and power density
plots for SeNCM-1000-OHzFCs and Pt/C-OHzFCs at 80 C. Testing conditions:
o
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Angewandte Chemie International Edition
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RESEARCH ARTICLE
the anolyte is 6.0 M KOH + 0.5 M hydrazine hydrate with a flow rate of 1 mL
min ; the catholyte is oxygen with a flow rate of 0.2 slpm. c) Long-term stability
of the SeNCM-1000-OHzFC.
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It is notable that much higher power densities at the high current
areas of SeNCM-1000-OHzFC were observed in comparison to
that of Pt/C-OHzFC, which can be attributed to the rapid mass
transfer throughout the hierarchical pore system as well as the
intrinsic bubble-repelling nanostructure surface31 of the SeNCM-
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1000 (Figure S29). Traditionally, the powdery nanocatalysts have
to be engineered into predefined shapes by mixing and pressing
with electronically insulating polymer binder (i.e. PVDF, Nafion) to
make them useful as practical electrode, which is a time/labour-
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[
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32
undesirable side-reactions in electrochemical devices . In
contrast, utilizing integrated SeNCM-1000 as binder-free
electrode for fabricating OHzFC (Figure S30-31) is extremely
appealing in terms of multiple merits, i.e. simplified electrode
fabrication craft and improved device performance and long-term
operational stability.
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Conclusion
In conclusion, we developed a facile way to fabricate large
scale, freestanding hierarchical porous carbon membrane with
atomically dispersed semi-metallic Se. The unique atomic
configuration of Se in membrane was for the first time determined
by integrated analytic methods. The membrane is proven to be
binder-free, high performance anode for HzOR in practical
OHzFC. This finding may aid the development of efficient single
semi-metallic atom catalyst for catalytic applications. We believe
that the membrane design platform described here will be
applicable to produce a broad range of functional porous carbon
membranes for practical applications, particularly those in energy
conversion devices that require heterogeneous membrane
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Acknowledgements
H. W. acknowledges the financial support from the Nankai
University, National Science Foundation of China (No. 21875119)
and State Key Laboratory of Coal Conversion, Institute of Coal
Chemistry, Chinese Academy of Sciences (J19-20-610). J. Y. is
grateful for financial support from the ERC Starting Grant NAPOLI
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Keywords: hydrazine oxidation • poly(ionic liquid) • atomically
dispersed selenium • porous carbon membrane
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This article is protected by copyright. All rights reserved.

Angewandte Chemie International Edition
10.1002/anie.201907752
RESEARCH ARTICLE
a
b
A scalable strategy to hierarchically
structured porous carbon membrane
containing atomically dispersed semi-
metallic selenium atoms has been
Tongzhou Wang , Qiang Wang ,
c
d
d
Yucheng Wang , Yunli Da , Wu Zhou *,
a
b
e
Yue Shao , Li Hou , Sihui Zhan , Jiayin
c
a
Yuan , Hong Wang *
developed.
The
membrane
is
demonstrated to function as binder-
free, high performance anode for
hydrazine oxidation reaction in
practical hydrazine fuel cell.
Page No. – Page No.
Title: Atomically Dispersed Selenium
on Porous Carbon Membrane as
Excellent Electrode for Hydrazine
Fuel Cell
This article is protected by copyright. All rights reserved.