In Situ Pyrolysis Tracking and Real-Time Phase Evolution: From a Binary Zinc Cluster to Supercapacitive Porous Carbon

Article abstract of DOI:10.1002/anie.202004072

The in situ tracking of the pyrolysis of a binary molecular cluster [Zn₇(μ₃-CH₃O)₆(L)₆][ZnLCl₂]₂ is presented with one brucite disk and two mononuclear fragments (L=mmimp: 2-meth

Full text of DOI:10.1002/anie.202004072

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Accepted Article
Title: In Situ Pyrolysis Tracking and Real Time Phase Evolution: from a
Binary Zinc Cluster to Supercapacitive Porous Carbon
Authors: Minghua Zeng, Yi-Fan Wang, Yiyu Liang, Yan-Fang Wu, Jian
Yang, Xu Zhang, Dandan Cai, Xu Peng, and Mohamedally
Kurmoo
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Angewandte Chemie International Edition
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ꢀ
In Situ Pyrolysis Tracking and Real Time Phase Evolution: from a
Binary Zinc Cluster to Supercapacitive Porous Carbon
[
a]
[b]
[b]
[a]
[a]
[b]
[a]
Yi-Fan Wang , Yiyu Liang , Yan-Fang Wu , Jian Yang , Xu Zhang , Dandan Cai , Xu Peng *,
Mohamedally Kurmoo and Ming-Hua Zeng[a,b]*
[c]
Abstract: We report the in-situ tracking of the pyrolysis of a binary
5 and ZIF-8 have been used as precursors,[6-7] which show
excellent properties due to the controllable pore size and
composition. The high surface area and high porosity of the
pyrolyzed MOF make it suitable for high-performance capacitive
energy storage applications.[8] Yet the tracking of the pyrolysis
process at the molecular level has not been challenged to
understand the relationship between synthetic conditions and
final functional products.[ In this regard, finding a well-designed
coordination structure to further realize the pyrolysis tracking in
real time is meaningful. Therefore, as a similar system, it is also
the desire to directly control the coordination molecular clusters
to obtain the material of the targeted structure for pyrolysis to
yield porous carbon materials with good supercapacitive
behavior.
molecular cluster [Zn
and two mononuclear fragments (L= mmimp: 2-methoxy-6-
(methylimino)-methyl)phenolate) to porous carbon using TG-MS
7 3 3 6 6 2 2
(μ -CH O) (L) ][ZnLCl ] with one brucite disk
(
from 30 to 900 °C. Following up the spilled gas product during the
decomposed reaction of zinc cluster along the temperature rising,
and in conjunction with XRD, SEM, BET and other materials
characterization, where three key steps were observed: 1) the
cleavage of the bulky external ligand; 2) the reduction of ZnO and 3)
the volatilization of Zn. Furthermore, the real time-dependent phase
sequential evolution of the remaining products and the processing of
9]
“
pore forming template” transformation are proposed simultaneously.
Introduced by above mechanism, the porous carbon structure
featuring a uniform nano-sized pore distribution synthesized at
2
-1
9
00 °C with the highest surface area of 1644 m ꞏg and pore volume
We have long-term experience in the study of the formation
and assembly process of transition metal clusters. Using the
3
-1
-1
of 0.926 cm ꞏg exhibits the best known capacitance of 662 Fꞏg at
-
1
0
.5 Aꞏg . The strategy of studying real-time phase evolution starting
knowledge acquired for related brucite disk-shaped [M
7
] clusters
and the mixed metal analogue [(Ni-
][10c] containing o-vanillin Schiff-base ligand and a range of
[
10a]
[10b]
from a well-designed cluster to a distinct nanostructure provides a
favorable approach to explore the potential high-performance energy
storage and conversion materials.
such as [Co
Co)
bridging ligands such, OH , CH
step-by-step assembly processes. Moreover, we recently design
7
],
7
[Ni ]
7
-
-
-
3
3
O or N , we have revealed their
2-
a Co
7
cluster with discrete [CoCl
3
N(CN)
2
]
anion, and achieve
High temperature reaction is accompanied by complex
chemical process, complicating and hampering tracking their
formation in real-time.[1] Therefore, in-depth knowledge of the
structural evolution process is of great importance for the design
of high-performance materials, connecting the structure-property
relationship between chemistry and materials. As representative
of products from high temperature pyrolysis in an inert
atmosphere, carbon materials derived from a wide variety of
high OER performance after controlled pyrolysis to cubic
metallic cobalt embedded in carbon. Therefore, to extend our
[11]
interest in this area we are investigating other coordination
compounds precursors of the o-vanillin Schiff-base ligand and its
derivatives. However, it is very rare that these high temperature
treatments leave carbon rich materials with minimal metal
content. As most metal oxides are very stable to fairly high
temperatures, they are not easily reduced to the metals, unless
under special reducing conditions. While this is true for many
metals of the periodic table, certain metal-oxides are easily
reduced to the respective metals under mild conditions.
Furthermore, only Zn (907 °C) can be vaporized at moderately
low temperatures (<1000 °C). Therefore, aiming to have a
carbon-rich porous structure, here, a heptanuclear zinc cluster
[2]
carbon-rich organic precursors have been widely studied. On
the one hand, controlling their accurate hierarchical structures
and effectively tracking their formation process methods are still
underdeveloped. On the other hand, controllable carbon-rich
materials with distinct structures witness versatile applications in
the fields of electrocatalysis,[ gas adsorption and energy
3]
[4]
storage.[5] Of note, metal organic frameworks (MOFs), i.e. MOF-
7 3 3 6 6 2 2
[Zn (μ -CH O) (L) ][ZnLCl ] (1) was obtained with exquisite
design orientation for this purpose. We therefore followed a
thorough study of its phase evolution under controlled
[
a]
Hubei Collaborative Innovation Center for Advanced Organic
Chemical Materials, Ministry-of-Education Key Laboratory for the
Synthesis and Application of Organic Functional Molecules,
College of Chemistry & Chemical Engineering, Hubei University,
Wuhan, 430062, P. R. China. E-mail: pengxu@hubu.edu.cn
atmosphere by monitoring the gas output using
a mass
spectrometer coupled to the thermogravimetry device (TG-MS),
and in conjunction with other materials characterization. Finally,
its electrochemical properties after removal of the metal by acid
etching found these porous carbon-rich materials exhibit high
capacitance (Scheme 1).
[
[
b]
c]
School of Chemistry and Pharmaceutical Sciences, Guangxi
Normal University, Key Laboratory for the Chemistry and
Molecular Engineering of Medicinal Resources, Guilin, 541004, P.
R. China. E-mail: zmh@mailbox.gxnu.edu.cn
Université de Strasbourg, CNRS-UMR7177, Institut de Chimie de
Strasbourg, 4 rue Blaise Pascal, Strasbourg 67008, France.
Supporting information for this article is given via a link at the end
of the document.
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Angewandte Chemie International Edition
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Scheme 1 Schematic illustration of the preparation procedure for 1 crystal to porous carbon underwent multiple phase evolution.
+
Analyses of the single-crystal X-ray diffraction data found it
coupled to the thermogravimetry device (TG-MS): CH
3
(m/z =
-
+
+
adopts the monoclinic space group P2
1
/c with a half of [Zn
7
L
6
(μ
3
-
15), CH
+
3
O (m/z = 31), CH
3
Cl (m/z = 50), CO
2
(m/z = 44) and
2+
-
OCH
3 6
) ]
cation (Zn
7
) and one [ZnLCl
2
]
anion (Zn
1
) per
Zn (m/z = 64, 66, 67, 68, 70). From these information, three
steps were identified in the process of decomposition: (a) ligand
decomposition; (b) reduction of ZnO; (c) evaporation of Zn. At
900 °C, almost all the Zn escapes due to its close boiling point
(907 °C), leaving a microporous carbon-rich structure (Scheme
asymmetric unit. The information of selected bond lengths and
angles are presented in Table S1b. The molecular structure
contains
mononuclear complexes. The cationic Zn
at the core by six μ -OCH and six peripheral oxygen atoms from
the η : η : η : μ bridged organic ligands. The six μ -OCH
a
heptanuclear disk cluster, and two identical
7
unit is held together
1),[7a] which has potential to be
a
high-performance
3
3
1
2
1
2
3
3
supercapacitive material.
bridged the outer Zn octahedra to the central Zn with three on
each surface forming the symmetric fragment of the brucite layer
and the six μ -O bridged pairs of zinc atoms at the edge of the
2
disk. Six nitrogen and six oxygen atoms from the corresponding
L ligands complete the peripheral ligation around the metallic
The unique discovery is not only the molecular structure of 1,
but also the thermal behavior under inert atmosphere during the
pyrolysis process with phase evolution. In light of the structure of
1 and the results monitored by TG-MS, the entire pyrolysis
process can be divided into several steps (Figure 1a). No
molecular fragments were detected while heating from 25 to
225 °C. The TGA confirms the absence of guest molecule in 1.
When the temperature is increased from 225 to 340 °C, the TG
shows a weight loss accompanying the departure of species
core. The bond lengths involving the μ
3 7 3
-O atom of the Zn (μ -
OMe) core range between 2.032 and 2.163 Å and the Zn-O-Zn
6
o
angles lie in the range 95.0-103.5 , while those involving the μ
2
-
o
]- anion has
O are in a narrower range 103.2-103.5 . The [ZnLCl
a tetrahedral Zn2 ion chelated by a Schiff-base ligand through
2
+
+
-
detected by TG-MS corresponding to CH
3
3
(m/z = 15), CH O
+
+
the imine nitrogen and phenol oxygen, and two chlorine atoms
(m/z = 31), CH
3
Cl (m/z = 50) (Figure 1b). Specifically, the CH
3
(
Figure S1
We expect that [Zn
,
Figure S2).
(μ
can be attributed to the cleavage of the ligand and the bridged
methoxy-labile ether bond in the cationic cluster (Zn ); the CH
O-
7
3
-CH
3 6 6
O) (L) ][ZnLCl
]
2 2
may determine its
7
3
functions after pyrolysis at high temperatures. To explore its
decomposition process, we captured the following key factors by
detecting the gas composition using a mass spectrometer
can be attributed to the cleavage of the methoxy group in the
+
anion (Zn
1
) ligand; the CH
3
Cl is produced by the combination of
a chlorine atom generated by cleavage of a Zn-Cl bond in an
Figure 1 (a) TG&DTG curves of 1 and the three processes that may be weight lost during pyrolysis from 1 to porous carbon; (b)-(d) The curves of
gaseous decomposition products (m/z = 15, methane; m/z = 31, oxygen methane; m/z = 50, chloromethane; m/z = 44, carbon dioxide; m/z =
6
4, 66, 67, 68, 70, zinc) derived from 1 pyrolysis process tracking by TG-MS.
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Angewandte Chemie International Edition
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ꢀ
anion (Zn
1
) with CH +
3
produced in the above process (Figure
temperatures basically maintain this shape (Figure S4). The
PXRD patterns (Figure S5) at different temperatures (600, 700,
800 °C) show the three products during pyrolysis displaying
strong diffraction peaks corresponding to ZnO, which is formed
by the oxidation of Zn filled in the pore structure.[ We also
found that ZnO particles were distributed on the surface and
inside (circled by the red dotted line in Figure S6) of the above
three pyrolysis products (Figure S7, Figure S8, Figure S9). It
should be noted that these ZnO particles with good crystallinity
diffused from the Zn in the channel to the surface during the
pyrolysis process and oxidized by air, which is consistent with
the ZnO peak founded in XRD pattern. For the 900 °C sample,
two broad peaks corresponding to carbon diffraction appeared at
2θ = 23° and 44°, which proved that the carbon material was
S3). Based on these analyses, the decomposition of one 1
molecule produces 8 CH , 4 CH Cl and 2 CH O . More
3 3 3
interestingly, it was found that the weight loss from TG data was
consistent with that of the calculation of peak intensities of each
fragment from TG-MS data (Table S2).
+
+
-
12]
Next, in the temperature range 480 to 570 °C, the weight loss
+
in the TG-MS is accompanied by only the departure of CO
2
(m/z = 44) (Figure 1c, Table S3). This stage may be a process
at which the core of 1 is converted to hexagonal ZnO, and
carbon at high temperature reduces ZnO to Zn. Above 570 °C,
five peaks (m/z = 64, 66, 67, 68, 70) (Figure 1d) were observed
which match the isotopic distribution for Zn . This indicates that
atomic zinc is generated by evaporation. At 900 °C by
approaching the boiling point of Zn (907 °C), almost all the Zn
+
[
7a] [13]
obtained as the pyrolysis temperature increased to 900 °C.
escape. The departure of Zn results in a porous carbon structure. Moreover, high resolution transmission electron microscopy
Moreover, it is worth noting that the rate of Zn evolution as
shown in Figure 1d is not constant, yet there is a rate-increasing
transition around 800 °C and the evaporation rate reaches a
maximum around 860 °C. This interesting phenomenon is
consistent with the TG that begins to accelerate weight loss after
(HRTEM), high-angle annular dark field (HAADF) and mapping
of 1-900 sample showed a disordered carbon layer with uniform
distribution of nitrogen and oxygen (Figure 2d, Figure S10),
rather than those observed for 1-800 forming ZnO particles
covered by amorphous carbon (Figure S11, Figure S12). Since
some of the ZnO are trapped in the pores of the pyrolyzed
products at 600, 700, and 800 °C, we use HCl acid to etch them
and to further investigate the change of pore structures. The
PXRD patterns of the pyrolyzed samples after etching are
shown in Figure 2a. Compared to the 900 °C sample, a similar
broad carbon diffraction peak appeared for 600, 700, and 800 °C,
and the R value of different samples is shown in Figure S13.
Besides, the degree of graphitization of the etched samples was
further characterized by Raman spectroscopy (Figure 2b). Two
8
00 °C and DTG has an extreme value at 860 °C. Therefore, we
selected four samples pyrolyzed at 600, 700, 800 and 900 °C to
study the pore generation process.
-
1
peaks were observed at 1329 and 1595 cm , which is attributed
to disordered structure/structural defects (or D-bands) and
graphite G-bands of carbon materials. In addition, the intensity
D G
ratio (I /I ) of the D to G band increases from 0.78 to 0.97 when
the temperature increases, indicating that the defect increases
with temperature, and saturates as 1-800* and 1-900 have the
D G
same I /I ratio. Also, X-ray photoelectron spectroscopy (XPS)
can effectively determine the chemical bonding properties of C,
N and O species in porous carbon. The XPS spectrum in Figure
2
c shows that the main peaks are at 284, 400, and 532 eV,
which can be assigned to C 1s, N 1s, and O 1s, respectively. It
should be noted that there was no significant change in the
percentages of the three bands in the four samples when
pyrolysis temperature increased, indicating that the composition
of the surrounded carbon may substantially stabilized (Figure
S14, Figure S15).[11] [14]
In order to further explore the pore carbon structure in
pyrolysis samples of pyrolyzed 1, nitrogen adsorption/desorption
measurement was performed a 77 K to extract the surface area
and pore size distribution (Figure S16). For the 1-900 sample,
the highest BET surface area and total pore volume were 1644
Figure 2 (a) Powder XRD, (b) Raman, and (c) XPS survey
spectrum of 1-600*, 1-700*, 1-800* and 1-900; (d) HRTEM of 1-900;
(
e) Total pore volume values, and (f) Pore size distributions
2
-1
3
-1
m ꞏg and 0.926 cm ꞏg , respectively. However, after acid
treatment, the three samples present BET surface areas of 641,
calculated from N adsorption isothermals for all samples.
2
2
-1
6
0
64 and 859 m ꞏg and total pore volume of 0.421, 0.437 and
In order to explore this pore structure derived from the
pyrolyzed 1, we conducted a series of characterization about
basic structural information. From the scanning electron
microscope (SEM) images, it can be seen that the shape of 1 is
a long hexagonal crystal, and the products at the four pyrolysis
3
-1
.478 cm ꞏg for 600, 700 and 800 °C pyrolysis samples,
respectively (Figure 2e). The pore size distribution of all
samples calculated from the nitrogen desorption using DFT
method (Figure 2f).
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Obviously, each sample has a narrow pore size distribution
around 0.5 nm. Since a large amount of pore volume is provided
by the space occupied by ZnO, and the increase in pore volume
is the fastest at about 0.5 nm, we consider that the pore size of
about 0.5 nm is what remains after Zn evaporates.[ When the
pyrolysis temperature is higher than 800 °C, the material
morphology produces more micropores with other pore sizes.
These micropores link with these 0.5 nm pores to accelerate the
evaporation rate of Zn, which is consistent with the curves
detected by TG and TG-MS. Finally, at 900 °C, almost all Zn
evaporates and the 1-900 has about 2 times the specific surface
show the CV curves of all samples at scan rates ranging from 5
to 100 mVꞏs-1 at -0.6~1.0 V. The approximate rectangular shape
of CV curves at different scan rates indicates ideal capacitive
behavior. It should be noted that an obvious redox peak is
detected ca. 0.3-0.4 V, which may be resulted from the redox
reactions of C=O group existed in the pyrolyzed samples, and
also consistent with XPS analyses.[ Figure 3b and Figure S18
are the GCD curves with a potential window from -0.6 to 1.0 V
for 1-900 electrode, exhibiting a specific capacitance of 662, 535,
474, 424, 395 Fꞏg-1 at current densities of 0.5, 1, 2, 5, 10 Aꞏg-1,
respectively, reaching the best value among the porous carbon
15]
16]
area and pore volume of other samples (Figure S16, Figure 2e). structures derived from MOFs and similar coordination structure
The specific surface areas of 1-900 are higher than other
pyrolysis samples, with the synergistic effect of larger pore
volume render 1-900 an excellent structure for electrochemical
energy storage.
(Table S4). We performed electrochemical impedance
spectroscopy test using a three-electrode configuration from 100
kHz to 100 mHz (Figure 3c). The EIS curves show a relatively
low equivalent series resistance of only 11.84 Ω for 1-900,
reflecting by the intersection of the curve at the real part at high
frequency region. Besides, the linear dependence at low
frequency region indicates ideal electric double layer behavior.
The specific capacitance and rate capability of 1-900 and other
pyrolyzed samples at various current densities (Figure 3d)
exhibit the superior supercapacitive performance, which is
mainly attributed to the synergic effect of reasonable pore size of
carbon materials produced at suitable pyrolysis temperature
favoring Zn evaporation. Furthermore, as shown in Figure 3e,
the specific capacitance was calculated from the CV curves
(
Equation S1), the value was comparable to that calculated
from the GCD curves[ and the contribution of the two process
of slow kinetics and fast kinetics at each temperature were
presented in Figure S19. Interestingly, the contribution of fast
kinetic (surfaced-controlled process) was also gradually
enhanced, which means the charge storage process was almost
not influenced by the ion diffusion process as the temperature
elevated.[17, 18] Combining with the discussion of BET analysis,
we conclude that the high temperature enhances Zn removal
5]
and simultaneously resulting in
a multi-dimensional inner
continuous pore distribution, thus shorting the ion diffusion
distance from the electrolyte into the electrode surface. Thus,
the charge storage process was greatly optimized toward a
supercapacitive charging rate. Figure 3f shows the excellent
cycle life of 1-900. After 5000 charge/discharge cycles, the
capacitance retention remained above 90%, indicating that 1-
9
00 has excellent cycle stability as a supercapacitor material. In
Figure 3 (a) Comparison of the CV at 5 mVꞏs-1 for all samples; (b)
Comparisons of the GCD curves at the current density of 0.5 Aꞏg-1 for
all samples; (c) Comparison of the electrochemical impedance
spectroscopy (EIS) for all samples; (d) Comparison of specific
capacitance values for all samples at different current densities; (e)
Histograms of the capacitance contributions by the different samples,
where purple is fast-kinetic processes and pink is slow-kinetic
processes. Meanwhile, Percentage represent the fast-kinetics
capacitance accounts for the overall capacitance ratio; (f)
Capacitance retention of 1-900 over 5000 charge/discharge cycles.
Inset: comparison of CD curves between the 1st CD cycle and the
addition, the coulombic efficiency of 1-900 is shown in Figure
S20. Thus, the route of controlled pyrolysis from suitable zinc
cluster to porous carbon material lead to excellent
electrochemical performance.
Conclusions
In summary, we present the synthesis and structure of the
unusual binary molecular Zn(II) coordination cluster, consisting
of a brucite disk alternating with two mononuclears. From 30 to
o
9
00 C, the step by step pyrolysis processing of above cluster
along with the progressive phase transformations as a function
of the temperature rising has been observed and explored using
in situ TG-MS, XRD, SEM, and BET. At 900 oC, it is the first
quantitatively monitor the evaporation of zinc metal under high
temperature and finally the zinc cluster evolved into the porous
carbon featuring uniform nano-size pore and narrow distribution
-
1
5
000th cycle for 1-900 at the current density of 5 Aꞏg .
To evaluate the electrochemical performance of pyrolyzed
samples from zinc cluster, we conducted cyclic voltammetry
CV), galvanostatic charge and discharge (GCD) and
electrochemical impedance spectroscopy (EIS) measurements
using three-electrode configuration, with Ag/AgCl as reference
electrode, for estimating the specific capacitance as
supercapacitor electrode materials. Figure 3a and Figure S17
(
2
-1
with the highest surface area of 1644 m ꞏg and pore volume of
3
-1
0
.926 cm ꞏg . As expected, the capacitance for sample treated
at 900 °C reaches 662 Fꞏg- at 0.5 Aꞏg , to our best knowledge,
1
-1
which records the best value among the porous carbon
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Angewandte Chemie International Edition
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ꢀ
structures. This first report of in situ pyrolysis tracking and real-
time phase evolution study of coordination cluster pave the way
for the decomposed mechanism, improvement of properties and
functions in novel hierarchical structure, especially derived from
well-designed coordination compounds, regardless of the
reticular structure of MOFs or the discrete molecular clusters.
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Mater. 2010, 22, 4295–4303; b) L. Q. Wei, K. Zhang, Y. C. Feng, Y. H.
Wang, M. H. Zeng, M. Kurmoo, Inorg. Chem. 2011, 50, 7274–7283; c)
H. X. Na, P. Y. Yang, Z. Yin, Y. H. Wang, L. X. Chang, R. Si, M.
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Acknowledgements
[
This work was financially supported by the National Science
Foundation of China for Distinguished Young Scholars (Grant
[
15] Y. L. Li, B. M. Jia, Y. Z. Fan, K. L. Zhu, G. Q. Li, C. Y. Su, Adv. Energy
Mater. 2017, 1702048.
21525101), the BAGUI talent program (2019AC26001), NSFC
[16] H. A. Andreas, B. E. Conway, Electrochim. Acta 2006, 51, 6510.
[
17] V. Augustyn, J. Come, M. A. Lowe, J. W. Kim, P. L. Taberna, S. H.
(
2
2
Grants 21805074 and 21661008), NSFC of Hubei (Grants
Tolbert, H. D. Abruna, P. Simon, B. Dunn, Nat. Mater. 2013, 12, 518-
017CFA006
and
2018CFB151),
NSFGX
(Grant
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4925-14931.
017GXNSFDA198040). MK was funded by the CNRS-France.
[
1
Keywords: Pyrolysis tracking; Binary zinc cluster; Phase
Evolution; TG-MS; Supercapacitive behavior.
--------------------------------------------------------------------------------------
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The in-situ pyrolysis and real time progressive phase evolution of a binary zinc molecular cluster are
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