From Metal-Organic Framework to Porous Carbon Polyhedron: Toward Highly Reversible Lithium Storage

Article abstract of DOI:10.1021/acs.inorgchem.7b01539

By application of a newly designed T-shaped ligand 5-(4-pyridin-4-yl-benzoylamino)isophthalic acid (H₂PBAI) to assemble with Zn(II) ions under solvothermal conditions, a novel porous polyhedral metal-organic framework (Zn-PBAI) with pcu topolog

Full text of DOI:10.1021/acs.inorgchem.7b01539

Article
pubs.acs.org/IC
From Metal−Organic Framework to Porous Carbon Polyhedron:
Toward Highly Reversible Lithium Storage
†
‡
‡
†
,†,§
and Yue-Peng Cai*,†
Hai-Jun Peng, Gui-Xia Hao, Zhao-Hua Chu, Ying-Lin Cui, Xiao-Ming Lin,*
†Guangzhou Key Laboratory of Materials for Energy Conversion and Storage, School of Chemistry and Environment, South China
Normal University, Guangzhou 510006, P. R. China
‡
College of Chemistry and Environmental Engineering, Hanshan Normal University, Chaozhou, Guangdong 521041, P. R. China
§Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South
China Normal University, Guangzhou 510006, P. R. China
*
S Supporting Information
ABSTRACT: By application of a newly designed T-shaped ligand 5-
4-pyridin-4-yl-benzoylamino)isophthalic acid (H PBAI) to assemble
(
2
with Zn(II) ions under solvothermal conditions, a novel porous
polyhedral metal−organic framework (Zn-PBAI) with pcu topology
has been obtained. When treated as a precursor by annealing of Zn-
PBAI at various temperatures, porous carbon polyhedra (PCP) were
prepared and tested as an anode material for lithium-ion batteries. The
results show that PCP carbonized at 1000 °C (PCP-1000) manifest the
−1
highest reversible specific capacity of about 1125 mAh g at a current
of 500 mA g− after 200 cycles, which is supposed to benefit from the
large accessible specific area and high electric conductivity. Moreover,
PCP-1000 electrode materials also exhibit superior cyclic stability and
good rate capacity.
1
1
7
18
1
. INTRODUCTION
nanostructured carbon, mesoporous carbon, and N-
19
modified carbon coated graphene have been investigated for
new electrode materials. In our previous work, we have
prepared a porous carbon microtube material by facile pyrolysis
of Cd-MOF {[Cd(HBTPCA)] H O} . As a continuous work,
herein, we designed and synthesized a novel T-shaped ligand, 5-
(4-pyridin-4-yl-benzoylamino)isophthalic acid ligand (H PBAI,
Figure S1), with pyridine and isophthalate groups connected
through amide group, to construct a porous Zn-based MOF
with pcu topology. Direct pyrolysis of this MOF gave rise to
porous carbon polyhedra, which could be used as anode
materials for LIBs with enhanced reversible capacity and
excellent cyclability.
Rechargeable lithium-ion batteries (LIBs), as one of the most
promising power sources, are widely used in portable electronic
devices. Among the diverse rechargeable batteries, carbon
materials are commonly used as anode for their low cost.
However, traditional graphite cannot meet the demands of
next-generation LIBs due to its low capacity of 372 mAh g .
Over the years, a great deal of research effort has been devoted
1
20
2
2
n
−1
2
2
to explore new high performance carbon anodes. Various3
carbonaceous materials, such as carbon nanotubes (CNTs),
4
5
6
carbon nanofibers (CNFs), nanospheres, nanosheets, nano-
7
8
9
cones, hierarchically porous carbon, graphenes, ordered
11,12
10
mesoporous carbon, and nitrogen/boron-doped carbon,
have been successfully prepared and applied as the electrode of
electrochemical energy devices. However, it still remains
difficult to produce carbonaceous materials with controlled
pore texture and improved capacity, which are considered to be
the important factors in optimizing the performance in LIBs.
Therefore, exploring and developing a novel method to prepare
carbon materials are urgently required.
2
. EXPERIMENTAL SECTION
2.1. Materials and Methods. Functional groups of the materials
were assessed using Fourier transform infrared spectroscopy (Thermo
Nicolet NEXUS 670 FT-IR, USA). A PerkinElmer 240 elemental
analyzer (USA) was used to record the elemental analyses. Crystalline
phase was identified by a Bruker D8 Advance X-ray diffraction pattern
diffractometer (BRUKER-AXS, Germany). Raman spectra were
obtained from a Renishaw inVia confocal Raman microscope (U.K.).
Netzsch Thermo Microbalance TG 209 F1 Libra (Germany) was used
for thermogravimetric analyses (TGA) in order to know the thermal
behavior (mass) of the material. The sorption isotherms were assessed
using a Belsorp max gas sorption analyzer (Japan) at 77 K. The surface
Interestingly, metal−organic frameworks (MOFs) consisting
of organic ligands and metal ions/clusters have emerged as
special functional solid-state materials for gas storage and
1
3
14
15
16
separation, catalysis, sensing, and drug delivery due to
their large surface area and tunable porosities. Recently, MOFs
have been successfully utilized as templates or precursors to
prepare porous carbon materials for applications in LIBs and
supercapacitors. Several novel carbon materials including
Received: June 17, 2017
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.7b01539
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Article
morphology and architecture were recorded by applying scanning
electron microscopy (SEM, TESCAN Maia 3, Czech). X-ray
photoelectron spectroscopy (XPS) was recorded by an ESCALAB
2
50Xi XPS spectrometer (USA). Varian Mercury Plus 300 MHz
1
spectrometer was used to record H NMR spectra (USA).
.2. Preparation of the Zn-PBAI MOF. To dimethylformamide
DMF, 6 mL) in a 20 mL scintillation vial were added Zn(NO ) ·
2
(
6
3
2
H O (14.9 mg, 0.05 mmol) and H PBAI (18.1 mg, 0.05 mmol). The
2 2
synthetic route of the H PBAI ligand is given in Figure S1 and further
2
1
confirmed by the H NMR spectrum (Figure S2). The vial was tightly
capped and heated in an 80 °C oven for 72 h. After cooling, colorless
block crystals were removed by filtration and dried in air (20 mg, 40%
−1
yield). FT-IR (KBr, cm ): 3447 (vs), 2348 (w), 1633 (m), 1545 (w),
294 (w), 770 (w), 623 (m), 483 (w). Anal. Calcd for C H N O Zn
1
26
30
4
9
(
607.89): C 51.33, H 4.92, N 9.21%. Found: C 51.26, H 4.97, N
.17%.
.3. Preparation of the Porous Carbon Materials. The porous
9
2
carbon polyhedral (PCP) materials were fabricated by annealing of the
as-synthesized Zn-based MOF particles under flowing nitrogen gas at
temperatures of 800 to 1000 °C. The resultant products were placed
under nitrogen atmosphere for 1 h. After the carbonization
temperature was retained in the tube furnace for 6 h, the materials
−
1
were cooled to room temperature at a rate of 1 °C min .
Subsequently, the obtained product was thoroughly washed by
hydrofluoric acid to remove all Zn elements. Finally, the sample was
washed three times with ethanol and dried at 70 °C to obtain the black
powder samples.
Figure 1. Crystal structure of Zn-PBAI. (a) Dinuclear Zn paddlewheel
motifs and coordination environment of ligand. (b) Octahedral cage.
(c) 3D metal−organic polyhedral framework. (d) Primitive cubic
network if the octahedra are regarded as octahedral nodes.
2
.4. Electrochemical Measurement. Test electrodes consisted of
the conductive carbon black (10 wt %), active powder material (80 wt
), and poly(vinylidene fluoride) (10 wt %). The slurry was formed
after thoroughly mixing the electrode components, and coated on
copper foil. Laboratory-made CR2032-type coin cells were fabricated
in an argon-filled glovebox with the separator (Celgard 2400), lithium
locate at each vertex (Figure 1b). These octahedral cages are
further connected by sharing the SBUs to give rise to a 3D
porous metal−organic polyhedral framework (MOP, Figures 1c
%
and S3), showing the hexagonal channel with open window of
2
9
.5 × 9.5 Å along the c axis (the centroid−centroid distances
metal, and electrolyte composed of 1 M LiPF in mixed solvent of
6
of the paddlewheels, Figure S4). If the SBB of the octahedral
cage can serve as an octahedral node, the whole framework
would be regarded as a primitive cubic topology (Figure 1d).
After removal of the guest molecules, the solvent-accessible
void is estimated to 36% as calculated by PLATON.
ethylene carbonate/dimethyl carbonate/diethyl carbonate (EC/
DMC/DEC, 1:1:1 in volume). Cyclic voltammetry (CV) curves
−1
were carried out at a scanning rate of 0.1 mV s (CHI605C
electrochemical workstation, voltage range: 0.01−3.0 V). The
electrochemical impedance spectra were tested by the same work-
station for various electrodes at 25 °C with the frequency between 100
kHz and 0.01 Hz.
3
.2. Characterization of Zn-PBAI MOFs. Scanning
electron microscopy (SEM) was first applied to observe the
morphology of the as-made Zn-PBAI MOFs. As seen in Figure
S5, the Zn-PBAI MOF particles show uniform shapes and sizes
overall: rhombic prisms with ca. 30 μm edges. In the IR
2
.5. X-ray Crystallographic Studies. X-ray reflection intensities
were collected on an Oxford Gemini S Ultra diffractometer equipped
with Cu Ka radiation (λ = 1.54178 Å) at 150 K by using ϕ and ω
21
scan. The empirical absorption correction was used to correct the
spectrum, the carbonyl band at 1716 cm− for H PBAI
1
reflections. The structure was solved by direct methods and refined by
2
2
22
full-matrix least-squares on F using the SHELXL program. Non-
hydrogen atoms were refined with anisotropic displacement
parameters at the final cycles. Isotropic displacement parameter was
used to place the organic hydrogen atoms in calculated positions. Due
to the highly disordered solvent molecules, as a result, we remove the
disappeared, indicating that the carboxylic groups of the ligand
were completely deprotonated (Figures S6 and S7). The
measured powder X-ray diffraction pattern (PXRD) was well
matched with the simulated one (Figure S8), indicating the
high phase purity of the samples, in which the preferred
orientation was reflected by the intensity differences. To
examine the thermal stability and behavior of Zn-BPAI, TGA
2
3,24
diffraction contribution by PLATON/SQUEEZE.
Crystallo-
graphic data for the structure is provided in Table S1, and selected
bond lengths and bond angles are listed in Table S2. CCDC 1523821
contains the supplementary crystallographic data.
measurements were conducted under N atmosphere (Figure
2
S9). The TG curve shows two major losses between 30 and 800
°
C. The weight loss of 64.51% during the first step (30−170
3
. RESULTS AND DISCUSSION
.1. Crystal Structure Description. Zn-PBAI crystallizes
in the space group of trigonal R3m and possesses a three-
°
C) corresponds to the release of two free DMF solvent
3
molecules and two guest H O moieties (exptl 30.4%, calcd
29.9%). Above 350 °C, the abrupt weight loss occurred,
indicating the decomposition of the whole frameworks.
2
̅
dimensional (3D) polyhedral framework with paddlewheel
Zn (COO) as the basic secondary building units (SBUs). As
3.3. Characterization of the Porous Carbon Materials.
The as-prepared crystalline samples were carbonized under N2
atmosphere at 800, 900, and 1000 °C, respectively. Then
resulting products were further washed using hydrofluoric acid
for 3 days to remove the residual Zn component.
Corresponding porous carbon polyhedra were designated as
PCP-800 (yield: 31%), PCP-900 (yield: 28%), and PCP-1000
(yield: 24%), respectively. Optical micrographs of Zn-PBAI and
2
4
shown in Figure 1a, two Zn ions are bonded by four carboxylate
functional groups to generate the paddlewheel SBU with a Zn−
Zn internuclear separation of 2.985(6) Å, while two N atoms
occupy the axial positions. Six Zn-paddlewheel motifs are linked
together by six PBAI ligands to give an octahedral supra-
molecular building block (SBB), in which six ligands cover the
alternating faces of the octahedron and the paddlewheel SBUs
B
DOI: 10.1021/acs.inorgchem.7b01539
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1
carbon material depicted in Figure S10 indicate that the
morphologies of PCP-800 and PCP-900 are similar to that of
PCP-1000. Therefore, only the morphology of PCP-1000 is
selected as a representative example. As shown in Figures 2a
peaks at 1599 cm− for G band and 1347 cm−1 for D band
(disordered carbon structure) were observed simultaneously. In
general, the intensity of D band increases when the number of
26
defects increases. The intensity ratios (R = I /I ) of D band
D
G
to G band for PCP-800, PCP-900, and PCP-1000 are 0.85,
0
1
.90, and 1.02, respectively. The greater I /I value of PCP-
000 than others indicates that the higher carbonization
D G
temperature generated more defects in the graphitic sheets.
To examine both the chemical composition and bonding
nature of the elements, X-ray photoelectron spectroscopy
(
3
XPS) spectra of the PCPs were analyzed as shown in Figure
c. The full XPS spectrum confirms the existence of O, N, and
C elements in all samples. Obviously, as the temperature rises
from 800 to 1000 °C, the N content increases to 4.64, 5.11, and
5
8
.33 atom %, while the C content decreases to 86.38, 85.15, and
3.72 atom %, respectively. The N 1s XPS spectrum in Figure
S11 can be deconvoluted into three peaks at 398.3 eV
(
(
pyridinic (N-6)), 399.7 eV (pyrrolic (N-5)), and 401.1 eV
graphitic N atoms). In the C 1s XPS spectrum (Figure S12),
27
the peaks at 288.6, 286.9, 285.7, and 284.7 eV correspond to
the nonoxygenated graphitic carbon, the oxygenated carbons,
carbonyl C, and carboxylate C, respectively.
28
Figure 2. SEM images of PCP-1000 at different magnifications. (a, b)
Polyhedral structure. (c, d) Rough surface with irregular gullies and
pores.
To better investigate the pore characteristics, nitrogen
adsorption−desorption isotherms of all three samples were
measured at 77 K. All isotherms follow the typical I curve which
is characteristic for microporous solids and exhibits steep
uptake and release of nitrogen gas at low pressure (Figure 3d).
The calculated porosity parameters and the pore size
distribution curves are presented in Table 1 and Figure S13.
and 2b, PCP-1000 shows similar shapes and sizes as those of
Zn-PBAI precursors. The high magnification SEM image
exhibits the rough surface of porous carbon polyhedron with
irregular gullies and pores (Figures 2c and 2d).
As presented in Figure 3, PXRD patterns suggest that PCP-
00, PCP-900, and PCP-1000 samples have similar diffraction
Table 1. Pore Characteristics of the Obtained Carbon
Particles
8
SBET (m g−1) Vtotal (cm g−1)
a
2
b
3
pore diameter (nm)
c
samples
PCP-800
PCP-900
PCP-1000
Zn-PBAI
1037
1160
1254
728
0.46
0.48
0.52
0.36
0.41
0.50
0.59
0.37
a
The specific surface area (SBET) was calculated by the Brunauer−
b
Emmet−Teller (BET) method.
V
represented the total pore
total
c
volume. Micropore size is calculated by the Horvath−Kawazoe (HK)
method.
Obviously, the parameters, which can affect significantly the
electrochemical performances of PCPs, increase as the
carbonization temperature rises from 800 to 1000 °C.
Compared with the porosity of Zn-PBAI precursor (BET of
2
−1
3
−1
7
28 m g , pore volume of 0.47 cm g , Figure S14), the
larger BET surface of PCPs not only provides a convenient
pathway to electrolyte diffusion and Li ion transfer but also
facilitates accommodating the volumetric variations during the
lithium storage process, which is highly favorable for the
electrochemical performance enhancement as electrode.
Figure 3. Prepared PCP-800, PCP-900, and PCP-1000 samples. (a)
PXRD. (b) Raman spectra. (c) Full XPS. (d) N sorption isotherms at
2
7
7 K.
3
.4. Electrochemical Analysis as an Anode Material.
features with two broad peaks at about 23° and 43°,
respectively, corresponding to the graphite (002) and (101)
peaks. The diffraction peak at 23° is characteristic of
graphitization degree in the graphitic carbon materials. No
other impurity signal was observed in the XRD pattern, which
indicates that the Zn species were completely removed by the
HF treatments.
To confirm our hypothesis that larger N contents, more
defects, and greater porosity are beneficial for providing more
active sites toward Li ions, the electrochemical behaviors of
PCP electrodes were discussed in detail. The charge−discharge
cycling performances of PCP-800, PCP-900, and PCP-1000
electrodes were evaluated in the range from 0.01 to 3.0 V at 0.5
A g (Figure 4). Obviously, the specific capacity increases
when the carbonization temperature rises from 800 to 1000 °C.
The electrodes still retained a discharge capacity of 1125 mAh
25
−1
Raman spectra of all three PCP samples are shown in Figure
b. Typically shown in amorphous carbon materials, two broad
3
C
DOI: 10.1021/acs.inorgchem.7b01539
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Inorganic Chemistry
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Figure 4. Cycling performance and Coulombic efficiency of PCP-800,
−1
PCP-900, and PCP-1000 at 0.5 A g for 200 cycles.
Figure 5. PCP-1000 electrode. (a) Discharge−charge curves from 0.01
−1
to 3.0 V at 0.5 A g . (b) Rate capability test. (c) Cyclic voltammetry
measurements during the first three cyclings. (d) Nyquist plots. The
inset is the proposed equivalent circuit.
g−1 (PCP-1000), 943 mAh g−1 (PCP-900), and 771 mAh g−1
(PCP-800) after 200 cycles, respectively. Stable and reversible
capacity can be observed and Coulombic efficiencies of all the
electrodes were more than 99% after the initial few cycles.
Compared with PCP-800 and PCP-900, the PCP-1000
electrode presents higher lithium storage and better cycling
stability, which mainly originated from the following reasons:
cathodic polarization process, a reduction peak at 0.52 V is
found, which might be ascribed to the SEI formation. During
the charge process, a wide oxidation peak at 1.36 V is detected.
The cathodic peak disappears in the subsequent two cycles, and
overlapping curves are observed, demonstrating that the
electrochemical reversibility is gradually built. Moreover,
electrochemical impedance spectra (EIS) of PCP-1000 were
investigated before and after 200 charge/discharge cycles in
order to get further insight into Li storage properties (Figure
5d). Similar curves for the two Nyquist plots are composed of a
high-frequency semicircle (SEI resistance), a medium-fre-
quency semicircle (charge-transfer resistance), and a low-
(
i) The electrical conductivities of PCP-800, PCP-900, and
−1
PCP-1000 are 10.2, 13.5, and 18.4 S cm , respectively. The
enhanced electrical conductivity facilitates the fast charge
transfer during the charge/discharge process. (ii) Temperature
is critical for the structural evolution of resultant PCP samples.
Higher carbonization temperature improves the accessible BET
surface area and provides more defects, which offered more
active sites for Li storage and increased the ability for the
accumulation of charges. (iii) As demonstrated in previous
literature, the amount of N-doping composition can improve
the Li storage capacity of the PCP materials to some extent.
29
33
frequency straight line (Warburg diffusion resistance). The
slightly decreasing depressed semicircle indicates that PCP-
1000 architectures reach a stabilized state and led to facile
charge transfer.
30
The N content of PCP-1000 (5.33 atom %) is larger than that
of PCN-900 (5.11 atom %) and PCP-800 (4.64 atom %).
Specifically, the total pyrrolic (N-5) N and pyridinic (N-6)
atoms are as much as 67 atom % in the PCP-1000 particles
4. CONCLUSION
(
Table S3), making the structure electron-deficient, which can
In summary, a novel Zn-PBAI metal−organic polyhedron with
a primitive cubic network was developed as template for
preparing porous carbon polyhedral material. When tested as
LIB anode material, PCP-1000 presents improved capacity of
more strongly bind lithium atoms and accept more charge from
Li ions.
As a representative example, electrochemical performances of
PCP-1000 will be described in detail. Figure 5a displays the
galvanostatic charge/discharge curves of PCP-1000 within a
cutoff window of 0.01−3.0 V at 500 mA g . The first discharge
capacity is 2156 mAh g , while the first charge capacity is 1316
mAh g . The large irreversible capacity loss with a low initial
Coulombic efficiency of 61.0% can be attributed to the
generation of a solid electrolyte interface (SEI) layer and
electrolyte decomposition. In addition, the rate performances
presented in Figure 5b show that the reversible capacities are
3
1
−1
1
125 mAh g . The enhanced electrochemical performance
could result from the unique porous structure, N-doping, and
high electrical conductivity. Many defects and large numbers of
pores in the obtained material would increase the active sites
−1
−1
−1
+
for Li storage.
ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b01539.
■
32
*
S
−1
−1
∼
1125, 1046, 850, and 698 mAh g at 0.5, 1, 2, and 3 A g ,
respectively. More importantly, the discharge capacity can
−1
−1
recover back to 1123 mAh g after deep cycling at 3 A g . In
comparison with other carbon hybrid materials (Table S4), the
PCP-1000 electrode presents higher Li storage properties. In
comparison with other porous carbon materials derived from
MOFs, PCP-1000 electrode shows competitive capacity and
superior rate capacity, demonstrating the excellent long-term
cycling stability for LIBs. Figure 5c shows the typical cyclic
voltammogram (CV) curves of PCP-1000 electrode. In the first
Details of experimental results, SEM image, FT-IR
spectrum, 1H NMR spectrum, PXRD pattern, TGA
curve, and XPS spectrum (PDF)
Accession Codes
CCDC 1523821 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_
D
DOI: 10.1021/acs.inorgchem.7b01539
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
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AUTHOR INFORMATION
■
*
*
Corresponding Authors
E-mail: linxm@scnu.edu.cn;.
E-mail: caiyp@scnu.edu.cn.
carbons for highly efficient CO capture: rational choice of a polymer
2
precursor. J. Mater. Chem. A 2016, 4, 17299−17307.
(14) Kang, Y.-H.; Yan, N.; Gao, Z.-Y.; Tan, P.; Jiang, Y.; Liu, X.-Q.;
ORCID
Sun, L.-B. Controllable construction of metal−organic polyhedra in
confined cavities via in situ site-induced assembly. J. Mater. Chem. A
Xiao-Ming Lin: 0000-0001-8835-103X
2
(
017, 5, 5278−5282.
Notes
15) Park, I.-H.; Medishetty, R.; Kim, J.-Y.; Lee, S. S.; Vittal, J. J.
The authors declare no competing financial interest.
Distortional supramolecular isomers of polyrotaxane coordination
polymers: photoreactivity and sensing of nitro compounds. Angew.
Chem., Int. Ed. 2014, 53, 5591−5595.
ACKNOWLEDGMENTS
■
(
16) Zheng, H.; Zhang, Y.; Liu, L.; Wan, W.; Guo, P.; Nystroem, A.
We are grateful for financial support from National Natural
Science Foundation of P. R. China (Grants 21401059,
M.; Zou, X. One-pot synthesis of metal-organic frameworks with
encapsulated target molecules and their applications for controlled
drug delivery. J. Am. Chem. Soc. 2016, 138, 962−968.
2
1471061, and 21671071), Innovation team project of
Guangdong Ordinary University (No. 2015KCXTD005),
Applied Science and Technology Planning Project of
Guangdong Province (Project 2017A010104015 and
(
17) Torad, N. L.; Hu, M.; Kamachi, Y.; Takai, K.; Imura, M.; Naito,
M.; Yamauchi, Y. Facile synthesis of nanoporous carbons with
controlled particle sizes by direct carbonization of monodispersed ZIF-
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