Research Article

pubs.acs.org/journal/ascecg

Synthesis of Vesicle-Like MgFe2O4/Graphene 3D Network Anode

Material with Enhanced Lithium Storage Performance
Yanhong Yin,*,†,‡,§ Wenfeng Liu,†,‡,§ Ningning Huo,†,‡,§ and Shuting Yang*,†,‡,§
†
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang Henan 453007, China
‡
National and Local Joint Engineering Laboratory of Motive Power and Key Materials, Xinxiang, Henan 453007, China
§
Collaborative Innovation Center of Henan Province for Green Motive Power and Key Materials, Henan Normal University,
Xinxiang, Henan 453007, China

ABSTRACT: Vesicle-like MgFe2O4/graphene 3D network

anode material was synthesized via a simple one-step in situ
growth of solvothermal technique. The as-obtained unique 3D
nanostructure consists of MgFe2O4 particles randomly anchored
on mutual cross-linking graphene sheets functioning as a
mechanical support and an efficient electron conducting pathway.
The as-synthesized anode material shows an excellent rate
capability and outstanding cycling stability. A specific capacity of
1300 mAh g−1 can be maintained at 1000 mA g−1 in a prolonged
charge/discharge process (200 cycles). When cycling at a high
current density of 10,000 mA g−1, a specific capacity of 597 mAh
g−1 can still be achieved. The superior battery performance can be
attributed to the unique 3D network structure, which provides an
efficiently conductive network, buffers the volume expansion, and improves the structure integrity of the electrode.
KEYWORDS: MgFe2O4, Graphene, Anode, Lithium ion batteries, Specific capacity

■ INTRODUCTION
Lithium ion batteries (LIBs) are one of the most promising
power supplies for electric vehicles (EVs) and hybrid electronic
vehicles (HEVs).1,2 In order to meet the increasing demands of
high energy density and long cycling lifetime, it is essential to
develop electrode materials with high charge/discharge capacity
and high-rate performance. Due to the low cost, high
theoretical specific capacity, and environmentally benign
nature, transition metal oxides (TMOs) are becoming
promising alternative anode materials for LIBs.3−6 Among
them, bicomponent transition metal oxides (AB2O4, A and B
denote divalent and trivalent metal cations, respectively) have
attracted increasing interests due to the relatively low activation
energy of electron transfer and rich redox reaction. Cations
with different valences accommodate in octahedral or
tetrahedral sites of the close-packed oxygen atoms, which can
synergistically enhance the intrinsic properties of each
component,7−11 such as electrical conductivity, electrochemical
reactivity, and mechanical stability.
MgFe2O4, consisting of high electrochemical active Fe2O3
and inactive MgO, can not only provide high specific capacity
but also relieve the volume expansion to a certain extent.
However, there are only few reports on the electrochemical
behavior of nanocrystalline MgFe2O4 as anode materials for
lithium ion batteries. Sivakumar et al.12 employed a high-speed
milling technique to prepare MgFe2O4 and first researched it as
anode material for lithium ion batteries, which achieved a high
discharge capacity of 1400 mAh g−1. Nevertheless, the
discharge capacity rapidly decreased to 300 mAh g−1 after
only 10 cycles. Then, Pan et al.13 synthesized MgFe2O4 by the
sol−gel method, and the capacity maintained only 493 mAh g−1
after 50 cycles. A modification technique was used to improve
the battery performance. Qiao et al.14 reported that MgFe2O4
nanofibers were synthesized by an electrospinning technique
and annealed at 800 °C. The obtained 1D MgFe2O4 nanofibers
showed an improved electrochemical performance with a
capacity of 714 mAh g−1 after 100 cycles. Gong et al.15 prepared
irregular MgFe2O4 nanoparticles (60 nm) via a coprecipitation
and calcining process, and then, MgFe2O4 and pyrrole were
added into autoclaves and heated at 550 °C for 5 h to obtain a
carbon-coated MgFe2O4. A specific capacity of 600 mAh g−1
after 50 cycles was obtained. Alok et al.16 prepared an
MgFe2O4/graphene nanocomposite through a urea-assisted
autocombustion method. The MgFe2O4 particles presented
serious aggregation on the graphene, whose capacity main-
tained 764.4 mAh g−1 at 0.04 C after 60 cycles. To date, there
still exists a big gap between the experimental and theoretical
specific capacities of MgFe2O4. Meanwhile, it is still very urgent
to improve their cycling and rate performances.
As the previous reports have shown, the poor performance of
MgFe2O4 is mainly caused by insufficient structural stability and
conductivity, which can be overcome through appropriate
Received: August 15, 2016
Revised: November 19, 2016
Published: December 5, 2016

© XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.6b01949

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Figure 1. Schematic illustration for the synthetic procedure of MFO/G.
morphology control and structure design.4,9,17−21 However, the
influences of morphology and structure on the electrochemical
performance are seldom investigated. As is well known, the
solvothermal technique is an effective method to prepare
materials via one-step in situ growth and to control the
morphology and structure by adjusting the reaction conditions.
Herein, vesicle-like MgFe2O4/graphene 3D network anode
material was designed and synthesized via a simple one-step in
situ growth of solvothermal techniques. In the target product,
the graphene layers cross-link with each other to form the 3D
conductive network, and the MgFe2O4 nanoparticles are
randomly anchored on both sides of the self-packaged graphene
sheets through electrostatic interaction. The 3D conductive
network can improve the conductivity, buffer the volume
expansion, and act as a barrier to suppress the aggregation of
active particles during the lithiation/delithiation process.18,22−25
As a result, the hybrid MgFe2O4/graphene electrode exhibits
high lithium-storage capacity, superior cycling stability, and
impressive rate performance. When cycling at 1000 mA g−1, a
specific capacity of 1300 mAh g−1 can be maintained after 200
cycles. When cycling at 10000 mA g−1, a specific capacity of 597
mAh g−1 still can be achieved.
■ EXPERIMENTAL SECTION
Materials Synthesis. Graphene oxide (GO) was synthesized
based on a modified Hummer’s method and then reduced as
previously reported.26,27 An exfoliated graphene suspension (100
mL, approximately 150 mg reduced graphene oxide) was obtained by
dispersing the reduced graphene oxide (rGO) in ethylene glycol (EG)
under ultrasonication for 2 h. 5 mmol of MgCl2·6H2O, 10 mmol of
FeCl3·9H2O, and 9 mmol of urea were added to the above suspension
under stirring. The mixture was transferred into a Teflon-lined
autoclave (80% degree of filling), subsequently heated at 200 °C for 24
h. The as-obtained MgFe2O4/grapheme (MFO/G) was washed with
deionized water and ethanol several times and dried in vacuum at 60
°C for 24 h. For comparison, bare MgFe2O4 (MFO) was also prepared
under the same conditions without reduced graphene oxide.
Materials Characterization. Powder X-ray diffraction (XRD)
patterns in the 2θ range of 20°−80° were obtained by Bruker AXS D8
using Cu Kα radiation (λ = 0.1541 nm). The morphology features of
the samples were characterized by the field emission scanning electron
microscope (FESEM, JSM-6700F). Transmission electron microscopic
(TEM) images were collected by a JEOL JEM-2100 microscope with
an accelerating voltage of 200 kV. X-ray photoelectron spectroscopy
(XPS) analysis was performed using a Kratos Axis Ultra spectrometer
with a monochromatic Al Kα radiation (hυ = 1486.6 eV). Thermal
gravimetric analysis (TGA) was used to measure the content of
graphene on a NETZSCH (STA 449 F3) thermal analyzer with a
heating rate of 10 °C min−1 in flowing air atmosphere. Raman spectra
were recorded with a Renishaw Invia spectrometer using a 532 nm
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laser line at room temperature. BET surface area and pore diameter
distribution were determined by Tristar 3020 analyzer at 77 K.
Electrochemical Measurements. The working electrodes were
prepared by mixing the active material (70 wt %), conducting agent
(Super P 20 wt %), and polyvinylidene fluoride (PVDF 10 wt %) well
in N-methyl-2-pyrrolidinone (NMP) solvent to form slurry, and then,
the slurry was brushed onto a Cu-current collector and dried at 60 °C
in vacuum for 24 h. The electrode was cut into discs 12 mm in
diameter and pressed at 6 MPa. The active material of each elctrode
was about 1.4 mg cm−2. CR2032 type coin cells were assembled in an
Ar-filled glovebox using Celgard 2400 as separator, Li foil as the
counter and reference electrode, and 1.0 M LiPF6 in ethylene
carbonate (EC)/dimethyl carbonate (DMC) (1:1 in volume) as the
electrolyte. Galvanostatic charge/discharge profiles between 0.01 and
3.0 V (vs Li+/Li) and rate capability at various current densities were
recorded on a LAND Cell test system (CT2001A, Wuhan, China),
and specific capacity of the composite was calculated by the total mass
of MgFe2O4 and graphene. Cyclic voltammograms (CV) and
electrochemical impedance spectroscopy (EIS) of the test cells were
carried out on an electrochemical workstation (CHI760E, Shanghai,
China). CV tests were performed between 0.01 and 3.0 V (vs Li+/Li)
at a scan rate of 0.2 mV s−1. The data of EIS were collected with a
frequency range from 0.1 Hz to 100 kHz and a signal amplitude of 5
mV.
■ RESULT AND DISCUSSION
Figure 1 illustrates our simple yet effective synthesis process of
MFO/G. Graphene was dispersed in ethylene glycol under
ultrasonication for 2 h, and then, metal salts and urea were
dissolved uniformly in the solution. During the solvothermal
reaction, urea decomposed into CO2 and NH3, which
interacted with Fe3+ and Mg2+ to form tiny spindle M(OH)-
CO3 crystal nucleii uniformly depositing on the graphene
sheets via electrostatic self-assembly. With reaction time
increasing, the tiny crystal nucleii coarsened to form irregular
spheres along with the pyrolysis of subcarbonate. Conse-
quently, under the effect of the Ostwald ripening, vesicle-like
MgFe2O4 nanoparticles were formed on the graphene sheets.
XRD patterns of as-synthesized MFO and MFO/G are
shown in Figure 2. All of the reflection peaks in the patterns can
be well indexed to the spinel-structured MgFe2O4 (JCPDS 88-
1939, Fd3̅m (227)). The diffraction peaks of 2θ at 30.0°, 35.4°,
37.1°, 43.1°, 47.2°, 53.4°, 57.0°, and 62.5° are ascribed to the
(220), (311), (222), (400), (331), (422), (511), and (440)
planes of MgFe2O4. Compared with bare MFO, the character-
istic diffraction peak at 26.3° in the MFO/G composite
confirms the existence of graphene layers, and all the
characteristic peaks in MFO/G become broad and weak,
implying a smaller grain size of MFO/G. The average grain
sizes of MFO and MFO/G calculated by the Scherrer equation
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Figure 2. XRD patterns of the synthesized MFO and MFO/G.
are 56 and 32.2 nm, respectively. The result can be due to the
existence of graphene sheets limiting the growth of MFO
particles during the synthesis process.
Morphologies and sizes of the MFO and MFO/G were
characterized by FESEM in Figure 3. Figure 3a and b show the
FESEM images of the MFO particles. The narrowly distributed
sphere-like particles aggregate together with some pinholes on
their surface, whose average particle size is about 160 nm.
Morphology of MFO in MFO/G (Figure 3c,d) is very similar
to that of the bare MFO, but the smaller average particle (about
100 nm) and better dispersity imply that the existence of
graphene can limit the growth and aggregation of MFO
particles. The MFO particles are randomly anchored on both
sides of the self-packaged graphene sheets, and the graphene
layers cross-link with each other to form the 3D network
structure.
Figure 4a and c show the TEM images of MFO and MFO/G.
In accordance with the FESEM results, MFO particles are
randomly anchored on both sides of the graphene sheets.
Interestingly, some transparent area can be observed on the
MFO particles, indicating that MFO particles are vesicle-like
Figure 3. FESEM images of MFO (a, b) and MFO/G (c, d) at different magnification.
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structures with many internal pores. The HRTEM image of
MFO (Figure 4b) demonstrates the interplanar spacing is 0.26
nm, consistent with the lattice fringe distance of the (311)
lattice plane of spinel MgFe2O4. Figure 4d displays a lattice
resolved HRTEM image of MFO/G. The lattice fringe spacings
of 0.27 and 0.31 nm are in accordance with the spacing of the
(311) and (220) crystal planes of MgFe2O4, respectively. The
winding lattice fringe spacing of 0.35 nm at the edge of the
particle corresponds to (002) planes of the graphene sheets.
Raman spectra and TG were used to obtain further
information on structure and composition of the samples.
Figure 5a is the Raman spectra of as-synthesized MFO and
MFO/G. For MFO, peaks at 475 and 684 cm−1 can be assigned
to the characteristic peaks of MgFe2O4,28−30 and the broad and
weak peaks at approximately 1330 and 1580 cm−1 can be
ascribed to the typical D and G bands of carbon materials
derived from the EG solvent of solvothermal. For MFO/G, the
characteristic Raman spectrum of MgFe2O4 becomes incon-
spicuous. While the characteristic peaks at ∼1350 cm−1 (D-
band), ∼1580 cm−1 (G-band), and ∼2730 cm−1 (2D-band)
become distinguishable, distinctly indicating that the MFO
particles are coated by graphene sheets. In addition, the weight
fraction of the rGO shown by thermogravimetric analysis
(TGA) (Figure 5b) is approximately 10.5 wt % in the final
composite. The weight of MFO increased slightly about 0.5 wt
%. It may be ascribed to a trace of Fe2+, which is too little to be
detected by XRD.
XPS analysis was performed to investigate the detailed
information about surface composition and electronic structure
of the samples. As indicated in the XPS survey spectrum
(Figure 6a), Mg, Fe, O, and C characteristic peaks, energy loss
peaks, and Auger electron peaks at different electron orbits or
transition states are observed for both MFO and MFO/G. The
deconvoluted C 1s peak (Figure 6b) was fitted to four
contributions (C1, C2, C3, and C4) for MFO/G. The C1 peak
at 284.7 eV and C2 peak at 285.6 eV can be assigned to the sp2
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Figure 4. TEM and HRTEM images of MFO (a, b) and MFO/G (c, d).
Figure 5. Raman spectra (a) and TG profiles (b) patterns of the synthesized MFO and MFO/G.
(C−C) and sp3 (C−O) hybridized graphite carbon, respec-
tively. The C3 peak at 287.3 eV might correspond to the
carbonyl and carboxylic (O−CO) groups. The C4 peak at
291.0 eV corresponds to either the carbonyl group or a π−π*
shake up satellite structure which is the characteristic of
conjugated systems.31−33
As shown in Figure 6c, the Fe 2p peak can be resolved into
two components (Fe 2p 1/2 and Fe 2p 3/2), which can be
deconvoluted into four peaks (marked with 1, 2, 3, and 4) using
Gaussian functions, corresponding to a tiny Fe2+ (B-site)
subpeak at 708.6 eV, Fe3+ subpeak at the A-site (710.8 eV),
Fe3+ subpeak at the B-site (712.6 eV), and the shakeup satellite
peak, respectively.34,35 From Figure 6d, it is obvious that the Fe
2p peak for MFO shifts to higher bonding energy after adding
graphene, which may be caused by the interaction between the
metal cation and the surface oxygenic functional groups of
RGO.
The porous feature of MFO and MFO/G was characterized
by the N2 adsorption−desorption measurement. In Figure 7,
both obtained nitrogen isotherm patterns present the typical
structural signature of type IV isotherm. For MFO/G, due to
the existence of a slit pore caused by the layer structure of
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graphene, the H3 type of hysteresis loop is formed within a
relative pressure P/P0 range of 0.4−1 between the desorption
and absorption isotherm, and its Brunauer−Emmett−Teller
(BET) specific surface area is calculated to be about 47.15 m2
g−1, which is higher than that of bare MFO (10.14 m2 g−1). On
the basis of the Barrett−Joyner−Halenda model, the pore size
of MFO/G distributes between 2 and 300 nm. The high surface
area of MFO/G with the meso- and macro-porous features is
benefit for electrolyte accessibility and rapid Li+ diffusion.
Cyclic voltammograms (CVs) of the MFO and MFO/G
electrodes are shown in Figure 8a−c. The CV curves of the two
electrodes are similar, indicating that a similar electrochemical
reaction occurs during the cycling process. As previously
reported,13,14,16 in the first cathodic scan, two reduction peaks
are observed at 0.6 and 0.1 V, corresponding to the reduction
of MgFe2O4 to Fe, MgO, and the formation of a solid
electrolyte interface (SEI) film layer on the electrode material
surface. In the first anodic scan, a broad peak is recorded
between 1.5 and 2.2 V, corresponding to a reversible oxidation
reaction. In the subsequent cycles, the two reduction peaks
slightly shift to ∼0.76 and 1.2 V, which can be attributed to the
structure transformation after the first cycle. Figure 8c shows
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Figure 6. XPS survey spectra of the synthesized MFO and MFO/G (a), the deconvoluted C 1s spectra (b) and Fe 2p spectra (c) of MFO/G, and
the comparison of Fe 2p spectra between MFO and MFO/G (d).
Figure 7. N2 adsorption−desorption isotherms and pore diameter
distribution of the as-synthesized MFO and MFO/G.
the comparison of the first two cycles of MFO and MFO/G.
Obviously, for the MFO/G electrode, the electrical potential
difference between the cathodic and anodic peaks is much
smaller than bare MFO, implying that reversibility of the
MFO/G electrodes is relatively better. This may be because
that adding high conductivity graphene can reduce the
electrodic polarization and improve the reversibility of
electrode process.
Figure 8d−f show the charge and dischage curves of the two
electrodes at a current density of 500 mA g−1 between 0.01 and
3.0 V (vs Li+/Li). It is found that the first discharge/charge
voltage profiles for the two electrodes are very similar, which
are consistent with their corresponding CV plots. In the first
discharge step, a rapid potential drop to 0.75 V is indicative of
partial Li+ inserting into the lattice to form LixMgFe2O4. The
voltage plateau at about 0.75 V corresponds to the conversion
reaction of Fe3+ to Fe2+ and Fe0. Subsequently, a sloping curve
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down to 0.01 V can be attributed to the formation of solid
electrolyte interface (SEI) film. After the first cycle, the voltage
plateau becomes less apparent. Instead, two sloping regions of
1.5−1.0 V and 1.0−0.75 V appear, in accordance with the CV
profiles, indicating that the structure transformation occurs
after the first complete cycle. With the cycling number
increasing, the MFO electrode (Figure 8d) shows an obvious
deterioration trend. The capacity decreases progressively (622,
388, and 331 mAh g−1 for the 30th, 50th, and 100th cycles,
respectively), and the polarization is increasingly severe.
However, the MFO/G electrode (Figure 8e) exhibits a slowly
enchanced reversible capacity (997, 1096, and 1341 mAh g−1
for the 30th, 50th, and 100th cycles, respectively). It is worth
noticing that, in comparison with the first and 100th discharge/
charge curves of the two electrodes (Figure 8f), when
introducing graphene, the MFO/G electrode appears to have
higher specific capacity and lower polarization. This may be
because graphene with large specific surface area increases the
contact area between the active material and electrolyte and
facilitates Li+ diffusion, and consequently, the electrodic
polarization decreases. Moreover, the better conductivity of
graphene and the smaller particle size of MFO in the composite
can also reduce the polarization.
Figure 9a−c show the cycle and rate performances of the
MFO and MFO/G at different current densities between 0.01
and 3 V. When cycling at a current density of 500 mA g−1
(Figure 9a), the initial discharge and charge capacities of the
MFO/G electrode are 1246 and 896 mAh g−1, respectively.
The corresponding Coulombic efficiency is 71.9%, and the
capacity loss can be attributed to the formation of SEI and the
irreverse insertion. Subsquently, the specific capacity shows a
continuous increase to 1341 mAh g−1 at the 100th cycle, with a
stable Coulombic efficiency higher than 98%. Notably, the
specific capacity of 1341 mAh g−1 is larger than the theoretical
value of MgFe2O4. The increased capacity is mainly due to the
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Figure 8. CV (a−c) and discharge/charge curves (d−f) of the synthesized MFO and MFO/G.

Figure 9. Cycling (a, b), rate performance (c), and EIS (d) of the synthesized MFO and MFO/G.

capacitance contribution from interfacial lithium storage and/or
reversible formation of polymeric/gel-like films.36−38 The initial
discharge and charge capacities of the bare MFO electrode are
1029 and 790 mAh g−1 with a relatively higher initial
Coulombic efficiency of 76.8%. However, its specific capacity
quickly fades. After 100 cycles, only 334 mAh g−1 (41.9%) is
retained. Importantly, the MFO/G electrode still exhibits a
superior cycling performance at the current density of 1000 mA
g−1 (Figure 9b). Specific capacity of the MFO/G electrode
appears to continually increase to about 1300 mAh g−1 at the
160th cycle and remains stable until 200 cycles, while capacity
of the bare MFO rapidly decays to 340 mAh g−1. Rate
performances of the two elecrodes are shown in Figure 9c with
current densities increased stepwise from 100 to 10000 mA g−1.
Obviously, the MFO/G electrode presents excellent rate
performance. At a current density of 100 mA g−1, the average
specific capacity of the MFO/G electrode is about 1080 mAh
g−1. Even cycling at 10,000 mA g−1, a capacity of 597 mAh g−1
F DOI: 10.1021/acssuschemeng.6b01949
and a capacity retention of 55.3% can still be retained, which is
more remarkable than the previous reports.13,15,16,39,40 More-
over, when the current density returns to 100 mA g−1, a
capacity of 1307 mAh g−1 can be attained again, which is even
higher than that of the first 10 cycles. Figure 9d shows EIS
measurements of the two electrodes after 50 cycles at 1000 mA
g−1. Both Nyquist plots of the two electrodes exhibit two
semicircles in the high-medium frequency range and an inclined
line in the low frequency range, corresponding to the SEI film
and contact resistance (Rs), charge transfer resistance (Rct)
between the electrolyte and active material, and the Warburg
impedance related to the solid-state diffusion of Li+ into the
bulk of the active materials.41,42 Apparently, the MFO/G
electrode shows a smaller semicircle diameter and a larger
inclined line, implying a relatively lower charge transfer
resistance and faster Li+ diffusion. This can be attributed to
the large specific surface area, high conductivity of the graphene
substrate, and smaller particle size of MFO in the composite,
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which not only increases the contact area between active
material and electrolyte and facilitates the Li+ and electron
transport but also shortens the pathway of Li+, leading to the
improved rate capability of MFO/G.
In summary, the 3D construction of vesicle-like MFO on the
graphene nanosheets contributes to a superior electrochemical
performance. First, introducing graphene can limit the growth
of MFO particles to form the smaller nanoparticles with a more
active site and shorten the pathway of Li+ diffusion. Second,
MFO/G composites with a higher specific surface area provide
more interfaces and better penetrability of the electrolyte.
Third, graphene can act as a 3D conductive network to improve
the electron transmission of the active material. Meanwhile,
graphene as a flexible matrix can buffer the volume expansion,
prevent the grain aggregate, and keep the electrode structure
integrity.
■
CONCLUSION
A spherical vesicle-like MFO/G hybrid system was synthesized
successfully via a simple one-step in situ growth of solvothermal
techniques. The graphene layers cross-link with each other to
form the 3D conductive network, and the MFO nanoparticles
are randomly anchored on both sides of the self-packaged
graphene sheets through electrostatic interaction. This unique
3D nanostructure can not only enhance the electrical
conductivity but can also buffer the volume expansion and
improve the structural integrity of the electrode. The MFO/G
electrode exhibits high lithium-storage capacity, superior cycling
stability, and impressive rate capability. This result shows that
the vesicle-like MgFe2O4/graphene 3D network hybrid system
is a promising next generation anode material for LIBs with
high energy and power density.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: yyh3326439@foxmail.com. Fax: (+86)-373-3326439.
Tel: (+86)-373-3326439 (Yanhong Yin).
*E-mail: shutingyang@foxmail.com. Fax: (+86)-373-3326439.
Tel: (+86)-373-3326439 (Shuting Yang).
ORCID
Shuting Yang: 0000-0001-7841-0016
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work is financially supported by the National Nature
Science Foundation of China under award (No. 21471049).
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H DOI: 10.1021/acssuschemeng.6b01949
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX