Nano Energy 97 (2022) 107146

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Nano Energy
journal homepage: www.elsevier.com/locate/nanoen

MOF-on-MOF nanoarchitectures for selectively functionalized

nitrogen-doped carbon-graphitic carbon/carbon nanotubes heterostructure
with high capacitive deionization performance
Ying Zhang a, Jingyu Wu a, Shuaihua Zhang a, b, *, Ningzhao Shang a, Xiaoxian Zhao a,
Saad M. Alshehri c, Tanir Ahamad c, Yusuke Yamauchi b, d, Xingtao Xu b, *, Yoshio Bando b, c, d, e, *
a
Department of Chemistry, College of Science, Hebei Agricultural University, Baoding 071001, Hebei, China
b
JST-ERATO Yamauchi Materials Space-Tectonics Project and International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials
Science (NIMS), 1–1 Namiki, Tsukuba, Ibaraki 305–0044, Japan
c
Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
d
Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane, QLD 4072, Australia
e
Australian Institute for Innovative Materials, University of Wollongong, Squires Way, North Wollongong, NSW 2500, Australia

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

Keywords: Carbon-carbon heterostructures are an emerging material paradigm to promote the development of capacitive
MOF-on-MOF nanoarchitectonics deionization (CDI). The synthesis of this heterostructure with designed functionalities derived from metal-
Capacitive deionization organic frameworks (MOFs) is interesting, but it has always been challenging. We develop MOF-on-MOF
Water desalination
nanoarchitectures to obtain a selectively functionalized nitrogen-doped carbon@graphitic carbon/carbon
Carbon nanotubes
Heterostructures
nanotubes heterostructure (NC@GC/CNTs) via the direct pyrolysis of elaborately designed ZIF-L@ZIF-67 core-
shell precursors. In this core-shell nanoarchitecture, the inner Zn-based ZIF-L provides a well-defined 2D
interface for the oriented growth of the Co-based ZIF-67 outer layer, which will then convert to NC nanosheets
with a high nitrogen doping content and large specific surface area for the accommodation of more ions.
Meanwhile, the outer ZIF-67 layer creates highly graphitized GC/CNTs architecture offering fast electron transfer
and good chemical stability, and it addresses the possible aggregation or collapse of the inner ZIF-L precursors
during pyrolysis. As expected, the newly developed NC@GC/CNTs material with well-designed functionalities
exhibits high salt adsorption capacity, rapid salt adsorption rate, and excellent CDI cycling stability, which
highlight the significance of the carbon–carbon heterostructure to potential CDI applications and the importance
of MOF-on-MOF nanoarchitectures on nanomaterials synthetic chemistry.

1. Introduction carbonaceous materials such as activated carbon (AC) [24,25], carbon

The increasing withdrawal and uneven distribution of freshwater
have become the most critical challenges to technological, economic,
and social developments along with the emerging global energy crisis
and environmental pollution [1–9]. The wide availability of seawater or
brackish water resources has resulted in saline water desalination
emerging as a sustainable strategy to address the freshwater shortage
[10–13]. Among many desalination techniques, capacitive deionization
(CDI), which removes ions via electrosorption [14–16] or pseudocapa­
citive reactions [17–20], is considered a promising alternative for
desalinating water at low salt concentrations [21–23]. Porous
aerogels [26], graphene [27,28], carbon nanotubes (CNTs) [29], and
biomass-derived porous carbons [30,31], have gradually become pri­
mary CDI electrode materials for realizing optimal CDI performance
[10]. However, low salt adsorption capacity (SAC) and rates continue to
remain the drawbacks of these carbon-based electrodes because of their
limited functionalities such as low effective surface area for ion elec­
trosorption, poor electrical conductivity, or narrow pore size distribu­
tion [10], all of which should be improved before utilizing them in
large-scale desalination applications.
A two-dimensional (2D) carbon–carbon heterostructure is an
emerging material platform for potential CDI application that possesses

* Corresponding author at: JST-ERATO Yamauchi Materials Space-Tectonics Project and International Center for Materials Nanoarchitectonics (WPI-MANA),
National Institute for Materials Science (NIMS), 1–1 Namiki, Tsukuba, Ibaraki 305–0044, Japan (X. Xu).
E-mail addresses: zhangshuaihua@hebau.edu.cn (S. Zhang), XU.Xingtao@nims.go.jp (X. Xu), Bando.Yoshio@nims.go.jp (Y. Bando).

https://doi.org/10.1016/j.nanoen.2022.107146
Received 8 January 2022; Received in revised form 11 March 2022; Accepted 12 March 2022
Available online 16 March 2022
2211-2855/© 2022 Elsevier Ltd. All rights reserved.
Y. Zhang et al.
unique advantages beyond common 2D carbon materials [32]. In prin­
ciple, the 2D carbon–carbon heterostructure can be prepared via coating
a layered polymeric precursor on a 2D carbon substrate with subsequent
pyrolysis. However, the investigated 2D substrate has mostly been
confined to graphene or reduced graphene oxide (rGO) [32], which not
only limits the diversity in the functionalities of the resulting hetero­
structures but is also unfavorable to the development of the nanocarbon
synthetic chemistry. Recently, the pyrolysis of metal-organic framework
(MOF) precursors/templates has demonstrated a new series of carbo­
naceous materials with controllable compositions, structures, and mor­
phologies [33–35]. The 2D zeolitic imidazolate frameworks (ZIFs), as a
subclass of MOFs, have received considerable research attention because
such 2D nanostructures can be considered a favorable choice as pre­
cursors to generate 2D porous carbon nanosheets with functionalities
beyond 2D graphene [36,37]. However, these 2D MOF nanostructures
are mostly confronted with structural instability, among which ZIF-8-L,
a typical 2D leaf-like architecture [38], is crystallized, where the Zn
node includes a free dangling monodentate ligand (2-methylimidazole,
MeIm) [39,40]. Thus, the pyrolysis of 2D MOFs easily experiences
ineluctable contraction, aggregation, or even collapse, and this conse­
quently results in the deteriorated 2D structure and decreased func­
tionalities, which further restricts their potential use as the substrate for
producing 2D carbon–carbon heterostructures [36,41]. Besides, the
engineered carbons from 2D ZIF-L are poorly graphited with abundant
defects or disorders, which induce poor cycling stability during
long-tern CDI use.
Recently, single MOFs with conductive skelecton have been devel­
oped as an important strategy to achieve enhanced electrochemical
energy storage performance and outstanding cycling stability [42–44].
As another cutting-edge approach, MOF-on-MOF nanoarchitectonics,
which includes core-shell MOF@MOF heterostructure construction, can
not only integrate both the advantages from the individual MOF
component, but also achieve enhanced structural stability and new ca­
pabilities that cannot be directly obtained with pristine MOFs [39,45].
Unfortunately, MOF-on-MOF nanoarchitectonics is mostly adapted to
construct 3D MOFs and their derived carbonaceous materials. In
response, we propose MOF-on-MOF nanoarchitectonics to prepare the
2D carbon–carbon heterostructure with designed functionalities. A
core-shell structured 2D ZIF-L@ZIF-67 can be obtained through the
Fig. 1. Schematic representation for the construction of the (A) leaf-shape ZIF-L and ZIF-L derived ZIF-L-C with a collapsed architecture, (B) ZIF-67 and ZIF-67
derived ZIF-67-C, and (C) leaf-shape core-shell structured ZIF-L@ZIF-67 and its transformation to NC@GC/CNTs.
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Nano Energy 97 (2022) 107146
oriented growth of ZIF-67(Co) on 2D ZIF-L(Zn), and then, it can be
adopted as the sacrificial template to generate the heterostructure of
nitrogen-doped carbon@graphitic carbon/carbon nanotubes (denoted
as NC@GC/CNTs). Fig. 1 schematically shows the formation of 2D ZIF-L
derived ZIF-L-C, 3D ZIF-67 derived ZIF-67-C, and NC@GC/CNTs,
respectively. The ZIF-L-C and ZIF-67-C demonstrate the different ad­
vantageous properties for CDI applications. The carbonization of ZIF-L is
expected to realize a sufficient amount of nitrogen dopants and large
specific surface area (SSA), featured with improved wettability and
tailored surface charges, which are all highly desirable for CDI elec­
trodes with high SAC [21]. However, the generation of disorders or
defects in the resulting ZIF-L-C, which refers to an amorphous carbon
structure, during the carbonization of ZIF-L can lead to poor CDI cycling
stability. In contrast, the ZIF-67-C architecture derived of ZIF-67 is ex­
pected to contribute a high-degree graphitized structure, which will
provide good electrical conductivity and stable CDI cycling perfor­
mance; however, its low SSA and N content still suffer from low CDI
performance [21]. Unlike the ZIF-L-C or ZIF-67-C from individual MOFs,
our NC@GC/CNTs prepared from the core-shell structured
ZIF-L@ZIF-67 can ingeniously integrate the advantageous properties of
both ZIF-L-C or ZIF-67-C. On the one hand, high nitrogen doping content
and large SSA from the pyrolysis of inner ZIF-L can afford a large number
of spaces and active sites for accommodating more ions. On the other
hand, the outer GC/CNTs can not only result in a high-degree graphi­
tized carbon layer for enhanced electron transfer and cycling stability
but can also effectively prevent the collapse of ZIF-L during pyrolysis.
Thus, the electrochemical measurements demonstrate that the
NC@GC/CNTs electrodes exhibit improved specific capacitance, excel­
lent charging/discharging characteristics, and low charge transfer
resistance. NC@GC/CNTs achieved a superior SAC, rapid salt adsorption
rate, and remarkable cycling stability when assembling into the CDI cell.
2. Results and discussion
The microstructures of the as-synthesized samples in each step were
characterized by scanning electron microscopy (SEM) and transmission
electron microscopy (TEM). In the beginning, 2D leaf-like ZIF-L (Fig. 2A,
B) with a thickness of about 186 nm (Fig. 2C) were prepared by mixing
the aqueous solutions of Zn2+ and 2-methylimidazole (MeIm).
Y. Zhang et al.
Fig. 2. SEM images of (A-C) ZIF-L, (D-F) ZIF-L@ZIF-67, and (G-I) NC@GC/CNTs. (J, K) TEM images of NC@GC/CNTs. (L) HRTEM images of CNTs and graphitic
carbons present in NC@GC/CNTs.
Subsequently, as presented in Fig. 2D-F, core-shell structured ZIF-
L@ZIF-67 nanoleaves were constructed from the room-temperature re­
action between Co2+ and MeIm through the assembly of ZIF-67 on the
surface of ZIF-L templates. Interestingly, the morphologies of ZIF-
L@ZIF-67 are slightly different to the original ZIF-L, and ZIF-L@ZIF-
67 nanoleaves exhibit an elongated hexagonal morphology with an
increased thickness (329 nm). Further, after coating ZIF-67 on ZIF-L
templates, the edge of the nanoleaves changes from a smooth surface
for ZIF-L (Fig. 2B) to an angled surface for ZIF-L@ZIF-67 (Fig. 2E). The
elemental mapping images of ZIF-L@ZIF-67 in Fig. S1 reveal the for­
mation of ZIF-L@ZIF-67 nanoleaves with a core-shell structure. In
addition, the SEM and TEM images of ZIF-L@ZIF-67 derived carbons,
NC@GC/CNTs, prepared by the pyrolysis of ZIF-L@ZIF-67 and the
elimination of the deposited Co or CoO species by H2SO4 etching shown
in Fig. 2G-J further illustrate that the leaf-like morphologies are well
preserved even after pyrolysis; this suggests our MOF-on-MOF synthetic
strategy successfully prevents the 2D architecture of ZIF-L from possible
collapsing or agglomerating during pyrolysis. For comparisons, Fig. S2-
S3 show the morphology and microstructure of carbon materials derived
from ZIF-L and ZIF-67. ZIL-L-C from pure ZIF-L nanoleaves tends to
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Nano Energy 97 (2022) 107146
agglomerate after pyrolysis because of the low structural stability of ZIF-
L (Fig. S2A, B) with an amorphous carbon state (Fig. S3A), whereas pure
ZIF-67-C exhibits 3D rhombic dodecahedron shapes with a distorted,
bumpy surface (Fig. S2C, D) and graphitic carbon structure (Fig. S3B).
The catalytic graphitization effect of well-dispersed Co species [46] in
the ZIF-67 shell of ZIF-L@ZIF-67 (see Fig. 2K, Fig. S3C), together with
the volatilization of the zinc element originating from the core of ZIF-L
during carbonization [47], leads to extensive CNTs generated on the
surface of graphitic carbon (Fig. 2L); this forms the well-developed
NC@GC/CNTs core-shell nanoleaves (Fig. 2J-L).
The crystalline structures of ZIF-L, ZIF-L@ZIF-67, and NC@GC/CNTs
were characterized by X-ray diffraction (XRD). As illustrated in Fig. 3A,
the characteristic peaks of the initial ZIF-L are consistent with those of
the simulated pattern of 2D ZIF-L and in good agreement with those in
previous reports [36,48]. For ZIF-L@ZIF-67, two groups of diffraction
peaks representing the ZIF-L and ZIF-67 phases are observed in the XRD
pattern. The newly prepared ZIF-L@ZIF-67 is then pyrolyzed at 800 ◦ C
under nitrogen followed by acidic etching for the construction of
NC@GC/CNTs. The XRD pattern in Fig. 3A indicates that the charac­
teristic peaks of ZIF-L and ZIF-67 disappear after carbonization; the
Y. Zhang et al.
Fig. 3. (A) PXRD patterns of simulated ZIF-L, experimental ZIF-L, ZIF-L@ZIF-67, simulated ZIF-67, NC@GC/CNTs, and metallic Co (JCPDS No. 15–0806). (B) Raman
spectra and (C) high-resolution N 1s high-resolution XPS spectra of NC@GC/CNTs700, NC@GC/CNTs800, and NC@GC/CNTs900. (D) Corresponding contents of
graphitic N, pyrrolic N, and pyridinic N in NC@GC/CNTsT at different carbonization temperatures.
diffraction peak at approximately 26◦ suggests the formation of the
graphitic carbon structure including the graphitic carbons and CNTs
[37], which matches well with the HRTEM images of NC@GC/CNTs
(Fig. 2L, S3C). Another two widened diffraction peaks at about 44◦ and
51◦ in the PXRD pattern of NC@GC/CNTs are assigned to the (111) and
(200) crystal planes of metallic Co (JCPDS No. 15–0806, a = 3.545 Å for
pure Co), respectively, possibly because Co nanoparticles cannot be
completely removed by H2SO4 etching and some remain with the sur­
rounding well-developed graphitic carbons [46,49]; this is confirmed by
the HRTEM image in Fig. S3 and the XPS spectrum in Fig. S4.
The ZIF-L@ZIF-67 was carbonized under different temperatures in
nitrogen atmosphere to harvest NC@GC/CNTs with different graphiti­
zation degrees, which are denoted as NC@GC/CNTsT (T: 700, 800, and
900 ◦ C), because the graphitization degree of carbonaceous materials
plays an important role in their practical CDI performance [21]; their
morphologies and compositions are illustrated in Fig. S5. Raman spectra
were applied to investigate the effects of the various carbonization
temperatures on the graphitization degrees of NC@GC/CNTsT. As
illustrated in Fig. 3B, three NC@GC/CNTsT samples show two charac­
teristic peaks with the maxima at ~1340 and 1580 cm− 1, which corre­
spond to the D-band and G-band of carbon materials, respectively. The
D-band originates from the defects at the edges of disoriented carbon
and the G-band is related to the ideal graphitic lattice. The relative ratio
of the calculated integrated areas for the D-band to the G-band, ID/IG,
represents the density of defects in the carbon lattice [48,49]. The values
of ID/IG exhibit a continuous decrease from NC@GC/CNTs700 (1.89) to
NC@GC/CNTs900 (1.14) with an increase in the carbonization temper­
ature, which suggests that a high temperature is favorable for the
transformation of the carbon atoms from the disordered state to the
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Nano Energy 97 (2022) 107146
ordered graphitic state [36]. Further, the carbonization temperatures
influence the N doping and Co contents in the derived NC@GC/CNTsT,
which further determine their CDI efficiency [21]. Fig. S5D shows that
the N and Co contents in NC@GC/CNTsT are gradually decreased from
6.31 to 4.23 at% and from 1.69 to 0.87 at%, respectively, as the pyrol­
ysis temperatures increase from 700 to 900 ◦ C. The binding states of
nitrogen in NC@GC/CNTsT were further revealed by the high-resolution
N 1s XPS spectra (Fig. 3C), and they can be deconvoluted into three types
of nitrogen species: pyridinic N (at 398.3 eV), pyrrolic N (at 399.5 eV),
and graphitic N (at 400.8 eV) [49,50]. The experimental results in
Fig. 3D exhibit that the relative contents of pyridinic N and pyrrolic N
gradually decrease from NC@GC/CNTs700 to NC@GC/CNTs900, whereas
the graphitic N contents are consistently promoted with an increase in
the pyrolysis temperatures. The CDI performances of NC@GC/CNTsT
with various pyrolysis temperatures were then evaluated in NaCl solu­
tion of 500 mg L− 1 at 1.4 V, whereas the SAC variations and CDI Ragone
plots of NC@GC/CNTsT in Fig. S6 illustrate that NC@GC/CNTs800 with
intermediate N and Co contents possess better CDI performances than
the NC@GC/CNTs700 and NC@GC/CNTs900 samples; this can be
attributed to its comparable graphitic-N ratio, and optimal N and Co
contents, which can result in the enhanced CDI performance.
A series of ZIF-L@ZIF-67 were prepared by regulating the amount of
ZIF-67 shell to the same amount of ZIF-L core, followed by pyrolysis at
800 ◦ C to harvest the corresponding NC@GC/CNTs, to investigate the
influence of the ratios of ZIF-L to ZIF-67 on the construction of the core-
shell ZIF-L@ZIF-67 nanoleaves and their derived NC@GC/CNTs. The
amount of the ZIF-67 shell portion was adjusted by varying the amount
of Co2+ (1, 2, and 4 mM) and MeIm (6, 12, and 24 mM), and the derived
NC@GC/CNTs from ZIF-L@ZIF-67 are labeled as NC@GC/CNTs1,
Y. Zhang et al. Nano Energy 97 (2022) 107146

NC@GC/CNTs2 and NC@GC/CNTs4, respectively. As shown in Fig. S7,
all NC@GC/CNTs samples possess 2D leaf-like morphologies; however,
the amount of CNTs on their surface increases with an increase in the
ratios of ZIF-67 to ZIF-L. Unlike the ZIF-L-C directly derived from ZIF-L,
nitrogen (N2) adsorption–desorption isotherms in Fig. S8A show that all
three NC@GC/CNTs samples possess hybrid type-I and type-IV iso­
therms with a steep N2 gas uptake at low relative pressures (P/P0 < 0.1);
this reveals the presence of micropores, whereas the hysteresis loops
ranging from 0.4 to 1.0 indicate the existence of mesopores in NC@GC/
CNTs. The pore size distribution profiles in Fig. S8B further show the
presence of the hierarchical micro-mesopore structures in NC@GC/
CNTs samples in comparison to the ZIF-L-C with a dominant micropore
structure. As indicated in Fig. S8C, ZIF-L-C has a low SSA of 149.2 m2
g− 1 attributed to the serious aggregation and collapse of the structure
during pyrolysis, and this unavoidably impedes the possible approach­
ability of ZIF-L-C to the electrolyte ions (Na+ and Cl-) during the CDI
process. As expected, NC@GC/CNTs achieves larger SSA and higher
porosity than ZIF-L-C, and NC@GC/CNTs2 possesses the largest SSA
(516.46 m2 g− 1) and the pore volume (0.21 cm3 g− 1), which demon­
strates that the introduction of ZIF-67 into ZIF-L can effectively reduce
its severe structural collapse, thereby forming a highly interconnected
pore connectivity channels favorable for accelerating the transport and
diffusion of electrolyte ion in CDI applications requiring fast charge/
discharge processes [51].
The NC@GC/CNTs possesses high SSA, hierarchical pore structure,
abundant active sites, and excellent conductivity, which are favorable to
CDI desalination. The electrochemical performances of the NC@GC/
CNTs electrodes were evaluated by cyclic voltammetry (CV) measure­
ments in a three-electrode system using a Pt counter electrode, an Ag/
AgCl reference electrode, and 1.0 M NaCl solution as the electrolyte. The
CV profiles at a scan rate of 100 mV s− 1 in Fig. 4A clearly show that
NC@GC/CNTs2 achieves larger values than those of NC@GC/CNTs1,
NC@GC/CNTs4, ZIF-L-C, and ZIF-67-C, which reflects its better capac­
itive performance. Further, this is clearly demonstrated from the gal­
vanostatic charge/discharge (GCD) curves of NC@GC/CNTs2 when
compared to those of the other samples at the same current density of

Fig. 4. (A) CV curves at 100 mV s− 1 and (B) GCD curves at 1.0 A g− 1 of NC@GC/CNT1, NC@GC/CNT2, NC@GC/CNT4, ZIF-L-C, and ZIF-67-C in 1.0 mol L− 1 NaCl.
(C) CV curves of NC@GC/CNT2 at different scan rates. (D) GCD curves of NC@GC/CNT2 at current densities from 0.5 to 10 A g− 1. (E) Specific capacitance at different
current densities. (F) Nyquist plots; (inset) High-frequency zoom-in region for NC@GC/CNT2, ZIF-L-C, and ZIF-67-C.

5
Y. Zhang et al.
1 A g− 1. As illustrated in Fig. 4B, the discharge time for NC@GC/CNTs2
is significantly enhanced than those of NC@GC/CNTs1, NC@GC/CNTs4,
ZIF-L-C, and ZIF-67-C, which further suggests NC@GC/CNTs2 offers the
largest charge capacity. Furthermore, the electrochemical performances
of NC@GC/CNTs and ZIF-L-C are evaluated by the CV and GCD curves
shown in Fig. 4C, D, and S9-S11. The nearly rectangular CV curves and
triangular GCD curves exhibit the capacitive behavior of NC@GC/CNTs.
The profiles about specific capacitance vs. current density in Fig. 4E
show that NC@GC/CNTs2 has a greatly improved capacitance and
enhanced capability in comparison with those of NC@GC/CNTs1,
NC@GC/CNTs4, ZIF-L-C, and ZIF-67-C. Electrochemical impedance
spectroscopy (EIS) was performed to investigate the electrochemical
behavior of NC@GC/CNTs (Fig. 4F, S9C, and S10C). Nyquist plots for
NC@GC/CNTs2, ZIF-L-C, and ZIF-67-C in Fig. 4F show that NC@GC/
CNTs2 has lower charge-transfer impedance than ZIF-L-C, evidenced by
the decreased diameter of the semicircle at high-frequency regime; this
suggests the good electronic conductivity of NC@GC/CNTs. The
experimental results of electrochemical measurements indicate that the
unique structure of NC@GC/CNTs can efficiently boost the capacitive
6
Nano Energy 97 (2022) 107146
performance of 2D ZIF-L derived carbons, which may render NC@GC/
CNTs architectures as a promising material for the CDI of saline water.
The CDI cells with a pair of NC@GC/CNTs electrodes were assem­
bled and studied at an operation voltage of 1.4 V in the NaCl concen­
tration ranging from 100 to 1500 mg L− 1 to further explore the CDI
performance of NC@GC/CNTs electrodes. As shown in Fig. 5A and S12,
the SACs of NC@GC/CNTs and ZIF-L-C increase sharply at first and then
reach the equilibrium state within all initial concentrations ranges.
Fig. 5B shows that the calculated SAC value of NC@GC/CNTs2 is
46.71 mg g− 1 at the 1000 mg L− 1 NaCl concentration, which is consid­
erably higher than that of NC@GC/CNTs1 (30.47 mg g− 1), NC@GC/
CNTs4 (37.35 mg g− 1), ZIF-L-C (24.63 mg g− 1), ZIF-67-C
(16.87 mg g− 1), and AC (10.94 mg g− 1). The corresponding Ragone
plots regarding to SAC vs. the mean salt adsorption rate (MSAR) in
Fig. 5C show that the plots of NC@GC/CNTs2 shift towards the upper
and more right region, which indicates NC@GC/CNTs2 achieves the
highest desalination performance and rate. Fig. 5D illustrates the SACs
of NC@GC/CNTs2, ZIF-L-C, and ZIF-67-C in the 1000 mg L− 1 NaCl so­
lutions with varying operation voltages from 0.8 to 1.6 V. The SACs of
Fig. 5. (A) SAC variations of the NC@GC/CNTs2 electrode
in different NaCl concentrations (operation voltage: 1.4 V).
(B) SAC variations and (C) CDI Ragone plots of NC@GC/
CNTs1, NC@GC/CNTs2, NC@GC/CNTs4, ZIF-L-C, ZIF-67-C,
and AC in 1000 mg L− 1 NaCl concentration (1.4 V). (D)
Comparisons of NC@GC/CNTs2, ZIF-L-C, and ZIF-67-C
with varying operation voltages ranging from 0.8 V to
1.6 V. (E) Langmuir isotherm and experimental data of
NC@GC/CNTs2 in the concentrations of NaCl solutions
ranging from 250 to 3000 mg L− 1. (F) CDI cycling perfor­
mances of NC@GC/CNTs2, ZIF-L-C, and ZIF-67-C in the
1000 mg L− 1 NaCl concentration.
Y. Zhang et al.
NC@GC/CNTs2, ZIF-L-C, and ZIF-67-C increase with an increase in the
operation voltage, and NC@GC/CNTs2 achieves an ultrahigh SAC value
of 56.30 mg g− 1 at 1.6 V, which is two times that of ZIF-L-C. According
to the Langmuir isotherm model analysis based on the CDI profiles of
NaCl concentrations ranging from 250 to 3000 mg L− 1 (Fig. 5E and
Table S1), NC@GC/CNTs2 achieves a maximum SAC value (qm) of
77.33 mg g− 1, which is obviously superior than most MOFs or MOFs
derived carbons-based CDI electrodes (Table S2).
Cycling CDI tests were conducted to evaluate the reversibility and
cycling stability of the NC@GC/CNTs2, ZIF-L-C, and ZIF-67-C electrodes
during the cycling electrosorption-regeneration processes in the
1000 mg L− 1 NaCl solution. As shown in Fig. 5F, ZIF-67-C achieves a
stable cycling performance with a high SAC retention ratio of 96.0% and
low SAC value of 16.19 mg g− 1 after 50 cycles, whereas ZIF-L-C pos­
sesses an unsatisfactory CDI cycling stability with sharply decreased SAC
retention ratio of 57.3% after only 20 cycles. NC@GC/CNTs2 exhibits
not only good cycling stability with a stable capacity retention ratio of
93.5% after 50 cycles but also a high SAC of 43.65 mg g− 1 after 50 cy­
cles. The excellent CDI performance of NC@GC/CNTs2 can be attributed
to the rationally designed core-shell nanoarchitectures with the syner­
gistic characteristics of the inner NC and outer GC/CNTs. As a control
experiment, we synthesized Co-ZIF-L nanoleaves (Fig. S13A) and
applied them as the template for the construction of Co-ZIF-L@ZIF-67
(Fig. S13B) and Co-ZIF-L@ZIF-67 derived carbons (GC@GC/CNTs,
Fig. S13C-E). The experimental results in Fig. S13F exhibit that NC@GC/
CNTs achieves larger SAC values than those of GC@GC/CNTs at any
operation voltage, which suggests the selection of ZIF-L(Zn) is crucial for
the fabrication of carbon electrodes with high CDI performance. In
addition, the morphological observations (Fig. S14A, B), XRD patterns
(Fig. S14C), and N2 adsorption-desorption isotherms (Fig. S14D)
confirm the excellent structural stability of NC@GC/CNTs after 50 CDI
cycles in saline water. Such high reversibility and good cycling stability
characteristics enable the NC@GC/CNTs architectures to satisfy the
demand of practical CDI applications.
3. Conclusion
In conclusion, NC@GC/CNTs have been synthesized using core-shell
structured ZIF-L@ZIF-67 nanoleaves as the self-sacrificial templates.
The prepared NC@GC/CNTs with well-defined GC/CNTs architectures
shows large SSA, hierarchical pore structure, and superior conductivity,
which is conductive to electrosorptive desalinations. Furthermore, the
NC@GC/CNTs-based CDI cell achieves high CDI performance with
excellent SAC, fast MSAR, and favorable cyclic stability. This work not
only furnishes a promising CDI electrode material for efficient desali­
nation applications, but also highlights a new avenue for preparing
novel core-shell MOF/MOF derived carbonaceous materials with
remarkable structural and compositional merits.
CRediT authorship contribution statement
Y. Zhang: Methodology, Formal analysis, Investigation, Writing –
original draft. J. Wu: Investigation, Formal analysis, Writing – original
draft. S. Zhang: Methodology, Project administration, Supervision,
Writing – original draft, Writing – review & editing. N. Shang: Inves­
tigation, Formal analysis. X. Zhao: Investigation, Formal analysis. S.M.
Alshehri: Resources, Investigation, Writing – review & editing. T.
Ahamad: Resources, Investigation, Writing – review & editing. Y.
Yamauchi: Funding acquisition, Writing – review & editing. X. Xu:
Supervision, Funding acquisition, Writing – original draft, Writing –
review & editing. Y. Bando: Supervision, Writing – original draft,
Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
7
Nano Energy 97 (2022) 107146
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was partially supported by the National Natural Science
Foundation of China (51909066, 22105059), JSPS Postdoctoral
Fellowship for Overseas Researchers (20F20338), the Scientific
Research Foundation for the Returned Scholars of Hebei Province
(C20200335), the Natural Science Foundation of Hebei Province
(C2020204136, B2019204009), and the JST-ERATO Yamauchi Mate­
rials Space-Tectonics Project (JPMJER2003). Yoshio Bando and Saad M.
Alshehri appreciate the Distinguished Scientist Fellowship Program
(DSFP) at King Saud University, Riyadh, Kingdom of Saudi Arabia for
the financial support. This work was performed in part at the Queens­
land node of the Australian National Fabrication Facility, a company
established under the National Collaborative Research Infrastructure
Strategy to provide nano and microfabrication facilities for Australia’s
researchers.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.nanoen.2022.107146.
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8
Y. Zhang et al.
Shuaihua Zhang received his PhD degree in 2016 from Hebei
Agricultural University. He is now an associate professor of
chemistry and has been awarded the honor of “Taihang
Scholar” at Hebei Agricultural University. Between 2018 and
2020, he joined in Prof. Yamauchi’s group as a postdoctoral
fellow at the International Center for Materials Nano­
architectonics (MANA), National Institute for Materials Science
(NIMS). His current research interests include nanostructured
functional materials and their application in capacitive deion­
ization and sustainable energy technologies.
Ningzhao Shang obtained his bachelor’s degree in 2012 and
master’s degree in 2015 from Hebei Agricultural University. He
is currently an Associate Professor at Hebei Agricultural Uni­
versity. His main research interests include the design and
synthesis of nanostructured hybrid materials and their appli­
cations toward energy conversion and storage.
Researchers in Chemistry in 2016–2021 and Materials Science in 2020–2021.
Xiaoxian Zhao received his PhD degree in 2018 from Uni­
versity of Science and Technology Beijing. After graduation, he
joined in Hebe Agricultural University as an associate professor
of chemistry and was awarded the honor of “Taihang Scholar”.
His current research interests include construction of inorganic
functional nano materials for energy storage.
Saad M Alshehri received his BSc from King Saud University in
1984, MSc from Northeastern University in 1989, and PhD in
Inorganic Chemistry from the Leicester University in 1992.
Currently, he is a Professor of Inorganic Chemistry at College of
Science, King Saud University, Saudi Arabia. Previously he was
the dean of the Riyadh Community College at King Saud Uni­
versity. His research focuses on the construction of nano­
structured, organic-inorganic hybrid materials for various
applications.
Nano Energy 97 (2022) 107146
Tanir Ahamad is presently a Professor in the Department of
Chemistry, College of Science, King Saud University (KSU),
Riyadh, Kingdom of Saudi Arabia. He obtained his PhD in
materials chemistry from Jamia Millia Islamia, New Delhi,
India in 2002 and 2006, respectively. He has a vast research
experience in the field of energy and environmental science. He
holds over 350 publications in reputed international journals
and several US patents. He has been named a Fellow of the
Royal Society of Chemistry (FRSC).
Yusuke Yamauchi received his bachelor’s degree (2003),
master’s degree (2004), and PhD (2007) from Waseda Uni­
versity, Japan. He then joined NIMS to start his own research
group. In 2016, he joined the University of Wollongong as a
full-time professor. He is currently a full-time professor at the
School of Chemical Engineering and the Australian Institute for
Bioengineering and Nanotechnology, The University of
Queensland, Australia. He concurrently serves as a group
leader of NIMS and as a visiting professor at Waseda Univer­
sity. His expertise is materials space-tectonics, and he has
published more than 950 papers with > 5,8000 citations (h-
index > 125). He has been selected as one of the Highly Cited
Xingtao Xu received his bachelor’s degree (2012) from Shan­
dong University and his PhD degree (2007) from East China
Normal University. From 2016–2017, he joined the Yamauchi
Group in NIMS, Japan, as an exchange PhD student. Subse­
quently, he started his independent research at Hohai Univer­
sity until he became a postdoctoral research fellow in NIMS
under the supervision of Professor Yusuke Yamauchi. In 2020,
he obtained a JSPS fellowship in NIMS. His research focuses on
the concept of materials space-tectonics for marine nanotech­
nology. He has published more than 100 papers with > 5700
citations (h-index = 44).
Yoshio Bando received his PhD degree from Osaka University
in 1975 and joined the National Institute for Research in
Inorganic Materials (presently NIMS) in the same year. From
1979–1981, he worked as a visiting researcher at Arizona State
University. He has been NIMS Fellow until 2018. Currently, he
is a distinguished scientist at King Saud University and hon­
orary professors at University of Wollongong and Queensland
University. His research focuses on the creation of various
inorganic nanostructured materials for energy applications and
their in-situ TEM study. He has published more than 900 papers
with > 64,000 citations (h-index 134).