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Organic–Rare Earth Hybrid Anode with Superior Cyclability

for Lithium Ion Battery
Jianwei Wang, Xiaolei Sun, Lingling Xu, Jiale Xia, Yaodong Yang, Zongyou Yin,*
Feng Luo, and Yaping Du*

new applications. Much effort is concen-

Organic compounds with electroactive sites are considered as a new generation trated on design and synthesis of novel
of green electrode materials for lithium ion batteries. However, exploring effec- electrodes that possess high theoretical
tive approaches to design high-capacity molecules and suppressing their solu- capacity, proper potential, and excel-
lent structural stability during long-term
bilization remain big challenges. Herein, a functional anode architecture is first
cycling.[2] Considering the sustainable
designed by using chemical bonds between organic compound and rare earth development, organic redox compounds
hollow structure, which enables active materials to be efficiently utilized, accel- with structural diversity should be ideal
erates reaction kinetics, and mitigates undesired dissolution in electrolyte. Com- electrode materials. However, organic
pared with pure organic sodium naphthyl-based tetrathiocarboxylate (SNBT) compounds frequently suffer from intrac-
compound and CeO2@Carbon, the hybrid electrode (CeO2@Carbon/SNBT) table technical challenges:[3] a) limited
electroactive sites for Li-ions insertion/
exhibits the best long-term cyclability and its capacity retention has significantly desertion cause low specific capacity; b)
increased. The current strategy would trigger more investigations into the devel- lithiated products are soluble in electro-
opment of organic materials for commercialized applications. lytes, leading to rapid capacity fading; c)
agglomerates of organic molecules cause
sluggish electrochemical kinetics.
1. Introduction To increase Li-ions storage sites, introducing redox func-
tional groups to organic compound represents one efficient
Lithium ion batteries (LIBs) have been dominating advanced approach to improve theoretical capacity.[4] For classical dicarbo-
energy conversion and storage technologies for the past xylic compounds as anode materials,[5] they reversibly transfer
20 years.[1] Tremendous commercial success motivated exten- two electrons during electrochemical processes. In other words,
sive research on reliable, non-toxic, low-cost, renewable, high- they reversibly intercalate two extra lithium ions in organic
energy density LIBs to satisfy ever-increasing demand for compounds during discharge process. In previous studies, we
have demonstrated that when four sulfur atoms are introduced
to a single carboxylate scaffold, electron delocalization and elec-
J. Wang, L. Xu, J. Xia, Prof. Y. Yang trical conductivity were remarkably improved. Accordingly, ion
Frontier Institute of Science and Technology
Xi’an Jiaotong University storage sites are significantly increased to six,[6] resulting in an
Xi’an 710054, China exceptional theoretical capacity.
Dr. X. Sun, Prof. Y. Du Although the problem of organic compound dissolution has
School of Materials Science and Engineering and National Institute been largely addressed by polymerization,[7] this approach relies
for Advanced Materials on the development of multicomponent polymeric reactions
Tianjin Key Lab for Rare Earth Materials and Applications
of small molecules. As for polymer battery, recent reports are
Centre for Rare Earth and Inorganic Functional Materials
Nankai University mainly focused on the field of π-conjugated polymer electrodes
Tianjin 300350, China such as polythiophene,[8] polypyrrole,[9] polyphenylene,[10] and
E-mail: ypdu@nankai.edu.cn polyacetylene.[11] Clearly, these polymers have no distinct redox
Prof. Z. Yin sites. As a result, their low doping-degrees lead to decreased
Research School of Chemistry theoretical capacities. Furthermore, most of the organic poly-
The Australian National University
Canberra ACT 2601, Australia mers display the morphology of agglomerates, which is not
E-mail: Zongyou.Yin@anu.edu.au conducive to the thermodynamics and kinetics of their elec-
Prof. F. Luo trode reactions. Fortunately, incorporating nanostructured
IMDEA Nanoscience conductors (e.g., carbon and metal oxides) to form compos-
Faraday 9 ites has been demonstrated as one effective strategy for pre-
Ciudad Universitaria de Cantoblanco
venting active material dissolution.[12] For instance, Zhang et al.
Madrid 28049, Spain
found that the carbon layer can improve electrical conductivity
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/admi.201902168. and the tangled CNT network can maintain the integrity of
composite electrodes (Si@C-CNTs).[13] Chen et al. used nano-
DOI: 10.1002/admi.201902168 structured magnesium nickel oxide (Mg0.6Ni0.4O) to prepare the

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CeO2@Carbon hollow spheres were prepared by mild hydro-

thermal reactions. In CeO2@Carbon/SNBT electrode mate-
rial, ceria has strong chemical binding and physical adsorption
with small organic molecules to firmly confine dissolution,
which could supply additional capacity. The thin carbon layer
enhances electrical conductivity. The hollow structure can well
alleviate structural strains and reduce effective diffusion dis-
tances for charges and ions. As a result, the capacity retention
of the hybrid material is enhanced by 27.0% after 120 cycles and
it exhibits superior electrochemical kinetics than SNBT. These
results would enlighten the use of organic molecules and inor-
ganic structure to build high-performance LIBs.

2. Results and Discussion

Scheme 1. Schematic illustrations for the formation of CeO2@Carbon/ 2.1. Characterization of Electrode Materials
SNBT.
Initially, sodium naphthalene-2,6-bis(carbodithioate) was syn-
sulfur/polyacrylonitrile/Mg0.6Ni0.4O (S/PAN/Mg0.6Ni0.4O) com- thesized by following the procedure of reduction, bromina-
posite via wet ball-milling. Mg0.6Ni0.4O powders promote the tion, and sulfuration on dimethylnaphthalene-2,6-dicarboxylate,
formation of the nanostructured composite and prevent sulfur which is one kind of an important raw material for fine chemi-
agglomeration upon cycling, improve the electrochemical cals and pharmaceutical products. The synthetic products of
kinetics, and enhance active sulfur utilization.[14] every step were characterized through liquid 1H and 13C nuclear
Rare earth metal oxide (CeO2) with good redox features (Ce3+/ magnetic resonance spectroscopy (NMR) and Fourier trans-
4+
Ce ), rich oxygen vacancies, high thermal stability, eco-friendly form infrared spectroscopy (FTIR). The corresponding results
nature, and low cost has been widely used in energy storage, (Figures S1–S6, Supporting Information) indicate the forma-
catalysis, gas storage, etc.[15] Many researchers have demon- tion of intermediates and the desired product with high purity.
strated that there exist strong physical adsorption and chemical Subsequently, CeO2 hollow spheres were prepared according to
bonding between CeO2 and polysulfides.[16] Herein, we first a previously reported method.[17] In order to improve the elec-
report a functional anode architecture by using chemical bonds trical conductivity of CeO2, an N-doped carbon layer was coated
between organic compounds and rare earth hollow structures. onto CeO2 hollow spheres by the carbonization of dopamine
The fabrication processes of hybrid nanostructures ceria@ precursor at 600 °C under Ar atmosphere.[18] As seen from
carbon/sodium naphthyl-based tetrathiocarboxylate (CeO2@ scanning electron microscopy (SEM) image in Figure 1a, the
Carbon/SNBT) are illustrated in Scheme 1. The novel SNBT CeO2@Carbon hollow spheres consist of many small carbon-
compound was synthesized by three-step reactions. Then, encapsulated CeO2 nanoparticles. Figure 1b shows that the

Figure 1. Characterization of CeO2@Carbon hollow spheres. a) SEM image; b) TEM and c) HRTEM images; d) HAADF image and EDS elemental
mappings of CeO2@Carbon. Characterization of CeO2@Carbon/SNBT. e,f) SEM images; g) SEM image and EDS elemental mappings.

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Figure 2. a,b) TGA analysis of SNBT and CeO2@Carbon/SNBT. Inset images show digital photos of the prepared SNBT and CeO2@Carbon/SNBT,
respectively; c) Raman spectra. The XPS spectra of Ce 3d region for d) CeO2@Carbon and e) CeO2@Carbon/SNBT; f) S 2p XPS spectrum of CeO2@
Carbon/SNBT.

CeO2@Carbon has uniform hollow nanostructures, whose inner peaks suggest that the hollow spheres are composed of many
diameter is about ≈200 nm. Nitrogen adsorption-desorption tiny particles, which is in good agreement with the results of
isotherms (Figure S7, Supporting Information) of the CeO2@ SEM and SAED. CeO2@Carbon/SNBT exhibits all character-
Carbon exhibit characteristics of type I/IV, which indicates the istic diffraction peaks of CeO2 and relatively strong diffraction
existence of tremendous mesopores. The corresponding pore peaks of SNBT.
size distribution was calculated by the Barrett–Joyner–Halenda Thermal decomposition temperature is an important index
(BJH) method and the CeO2@Carbon has narrow pore size for electrode materials. Therefore, thermogravimetric analysis
distributions and the peak of mesopores is located at ≈3.7 nm. (TGA) measurements were performed in air at a heating of
The calculated Brunauer–Emmert–Teller (BET) surface area 10 °C min−1. The CeO2 content is 94.6% in CeO2@Carbon and
of the CeO2@Carbon is about 115.4 m2 g−1, which is highly 64.8% in CeO2@Carbon/SNBT (Figure S10, Supporting Infor-
conducive to the surface and near-surface reactions. High- mation). Compared with the SNBT (Figure 2a), the decom-
resolution transmission electron microscope (HRTEM) was position temperature of the CeO2@Carbon/SNBT hybrid
used to measure interplanar spacing of 0.31 nm (Figure 1c), electrode (Figure 2b) increases by 30 °C, which indicates the
which is well indexed to CeO2 (111) planes. Remarkably, a thin existence of strong interfacial bonding between SNBT and
carbon layer is observed at the outermost layer and its thickness CeO2@Carbon.[19] The SNBT powder is dark yellow, while the
is approximately 2 nm. In addition, high-angle annular dark- composite of CeO2@Carbon/SNBT turns black. As shown
field (HAADF) image and energy-dispersive X-ray spectroscopy in Figure 2c, Raman spectroscopy was used to investigate the
(EDS) elemental mappings of the CeO2@Carbon were collected. three kinds of electrode materials. For the CeO2@Carbon mate-
As shown in Figure 1d and Figure S8a, Supporting Informa- rial, typical D and G peaks at 1359 and 1576 cm−1 (ID/IG = 0.94)
tion, Ce, O, C, and N elements are distributed homogeneously justify the existence of the carbon layer. One weak peak at 454
in the hollow spheres. Selected area electron diffraction (SAED) cm−1 is also observed, which is attributed to pure CeO2 nano-
pattern (Figure S8b, Supporting Information) further reveals particles. The results indirectly prove that the N-doped carbon
that lots of spots are arranged in circular rings, which confirms layer is very thin, which is in good agreement with the HRTEM
the polycrystalline nature of CeO2 nanoparticles. Afterward, result. Furthermore, the SNBT material exhibits characteristic
the CeO2@Carbon/SNBT composites were prepared through a peaks at 1166, 1390, 1908, 2056, 2195, and 2383 cm−1. Impor-
facile hydrothermal method. SEM images (Figures 1e,f) reveal tantly, CeO2@Carbon/SNBT hybrid material shows character-
that the SNBT is evenly bonded to the surface of the CeO2@ istic peaks of CeO2@Carbon and SNBT simultaneously; its D
Carbon. Additionally, Figure 1g clearly demonstrates a homo- and G peaks are 1389 and 1598 cm−1 (ID/IG = 0.90), respectively.
geneous distribution of Ce, S, N, Na, and O within the CeO2@ Compared with CeO2@Carbon, D and G peaks of CeO2@
Carbon/SNBT hybrid nanostructures. Powder X-ray diffraction Carbon/SNBT migrate significantly; its value of ID/IG decreases
(XRD) patterns of the three materials are revealed in Figure S9, slightly, which could be due to the strong interfacial bonding
Supporting Information. Clearly, CeO2@Carbon shows charac- consistent with the TGA results.[20]
teristic diffraction peaks of CeO2, which can be well indexed to X-ray photoelectron spectroscopy (XPS) was further con-
the fluorite structure (PDF#34-0394). These broad diffraction ducted to explore chemical environment of surface. The XPS

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spectra of Ce 3d for CeO2@Carbon and CeO2@Carbon/SNBT discharge/charge curves, there is also no obvious plateau after
materials are deconvoluted into eight peaks with the assign- the initial discharge (Figure S11, Supporting Information), only
ment defined in Figure 2d,e, respectively. The peaks labeled v3 a long slope below 0.3 V, suggesting the existence of capacitive
and u3 represent the 3d104f1 electronic state of Ce3+ and other behavior. These discharge/charge results are in good accordance
peaks labeled v1, v2, v4, u1, u2, and u4 represent the 3d104f0 elec- with the CV results. Based on the low-average voltage, three
tronic state of Ce4+.[21] The results show that both Ce3+ and Ce4+ electrodes will be competitive materials as anodes for LIBs.
exist in the two materials, which indicates the redox nature Among these electrodes, the CeO2@Carbon shows the lowest
of materials. The presence of Ce3+ ions could lead to charge discharge capacity of 341 mAh g−1, yet the SNBT and CeO2@
imbalance, creating oxygen vacancies and unsaturated chem- Carbon/SNBT have similar capacities (443 and 425 mAh g−1),
ical bonds in CeO2 lattice.[22] As is known, the concentration of which clearly indicates that the inorganic components (CeO2@
Ce3+ ions would be estimated from the equation[23] as follows: Carbon) do not significantly change the discharge capacity of
ρ(Ce3+) = [A(Ce3+)]/[A(Ce3+) + A(Ce4+)]. According to the calcu- the CeO2@Carbon/SNBT material.
lation, ρ(Ce3+) in CeO2@Carbon and CeO2@Carbon/SNBT are Strikingly, as shown in Figure 3c, the long-term cyclability of
30.9% and 25.3%, respectively. The concentration of Ce3+ in the CeO2@Carbon/SNBT material is significantly enhanced com-
CeO2@Carbon/SNBT is decreased by 5.6%, which evidentially pared to that of the other two electrodes. After 120 cycles, the
proves that SNBT anions bond strongly with CeO2 at the inter- capacity retention of the CeO2@Carbon/SNBT is as high as
face to induce the charge redistribution. Figure 2f shows that 75.2%, which is much higher than that of the SNBT (48.2%).
the S 2p spectrum of the CeO2@Carbon/SNBT is fitted into six Thus, the low capacity retention of the SNBT is caused by
peaks at 167.9, 166.7, 165.6, 162.8, 161.6, and 160.4 eV, respec- the dissolution of lithiated products. As for CeO2@Carbon,
tively. It is worth noting that the two fitting peaks at 167.9 and it remains 119 mAh g−1 after 120 cycles. In Figure 3d, the
166.7 eV could be assigned to the bonds of Ce-SOx-C,[24] sug- rate capabilities of the three electrodes were evaluated at cur-
gesting the effective bonding of S atoms in SNBT with Ce and rent densities from 50 to 1000 mA g−1. Compared with other
C atoms in CeO2@Carbon. two electrodes, the CeO2@Carbon/SNBT exhibits the highest
discharge/charge capacities at various current densities. The
significant enhancement in electrochemical performance for
2.2. Electrochemical Performance CeO2@Carbon/SNBT is mainly attributed to the strong chem-
ical bond and physical absorption of CeO2 to effectively block
Electrochemical measurements were performed to investigate the lithiated SNBT material within the electrode region.
the battery performance of the as-prepared materials for LIBs. To demonstrate the architectural advantages of the CeO2@
Figure 3a reveals cyclic voltammetric (CV) curves of the three Carbon/SNBT, continuous CV curves and electrochemical
electrodes in the voltage range of 0–3 V (vs Li/Li+) at a scan impedance spectroscopy (EIS) measurements were conducted
rate of 1.0 mV s−1. As for three electrodes, broad oxide peaks to evaluate Li storage performance. Figure 4a,d exhibits CV
are displayed in the low potential region (0–0.3 V) and no curves of the SNBT and the CeO2@Carbon/SNBT electrodes at
obvious reversible redox peaks can be observed. In Figure 3b, different scan rates in a half cell. As the scan rate increases, the
the lithium storage properties of the three electrodes were shapes are well preserved. Generally, voltammetric sweep rate
evaluated by galvanostatic discharge/charge measurements. In is used to quantitatively analyze the capacitive contribution to

Figure 3. Electrochemical performance of the electrodes. a) CV curves at a scan rate of 1.0 mV s−1; b) galvanostatic charge/discharge curves; c) cycling
stability at 200 mA g−1; d) rate capability.

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Figure 4. Quantitative capacitive analysis of lithium storage behaviors. a,d) CV curves at different scan rates. b,e) Capacitive contribution and diffu-
sion contribution at 1.2 mV s−1. c,f) Normalized contribution ratio of diffusion-controlled capacities at different scan rates. g,h) EIS profiles at different
depths of discharge (vs Li/Li+); i) Bode plots of SNBT and CeO2@Carbon/SNBT electrode.

the current response, which can be expressed as the following at interface and mass transfer of lithium ions, respectively.[26]
equation[25]: i(V) = k1ν + k2ν1/2, where i is the current response, In general, the larger diameter of the semicircle means a larger
k1ν represents capacitive effects and k2ν1/2 stands for diffusion- charge transfer resistance.[27] In the high-frequency domain,
controlled insertion at the corresponding voltage (V). As a the apparent differences of radius at the same potentials indi-
result, the capacitive contribution makes up about 24.0% of the cate that the architecture of the CeO2@Carbon/SNBT facili-
total capacity for the SNBT electrode at 1.2 mV s−1 (Figure 4b). tates rapid charge transfer. Furthermore, the steeper line of the
However, for the CeO2@Carbon/SNBT composite electrode CeO2@Carbon/SNBT suggests rapid transfer of lithium ions.
(Figure 4e), this value increases to 35% at the same scan rate. Bode plots of two samples (Figure 4i) at 3.0 V were also used to
In addition, their capacitive contribution is gradually increased estimate the Li+ diffusion kinetics in electrode materials. Rele-
with the increase of the scan rate (Figure 4c,f). Clearly, the vant reports have demonstrated that the ion diffusion is related
value of capacitive contribution for the CeO2@Carbon/SNBT to the phase angle in the low-frequency region and the smaller
is higher than that of the SNBT electrode at the corresponding the phase angle, the faster the ion diffusion.[28] The CeO2@
scan rate. The remarkable enhancement is attributed to the Carbon/SNBT shows a smaller phase angle, suggesting a faster
unique hollow architecture, which could provide a rich supply ion diffusion process.
of surfaces/interfaces, allow electrolyte to easily penetrate into
the outer/inner layers, and rapidly transfer Li ions and elec-
trons to redox active interfaces, leading to excellent rate capabili­­ 3. Conclusion
ties and electrochemical kinetics. Figure 4g,h shows EIS pro-
files of the SNBT and CeO2@Carbon/SNBT at different depths In summary, a novel tetrathiocarboxylate molecule is success-
of discharge, respectively. Nyquist plots display a compressed fully synthesized as one kind of potential high-capacity elec-
semicircle in high-frequency region and a straight line in low- trode material. Meanwhile, CeO2 hollow spheres coated with a
frequency region, corresponding to charge-transfer resistance thin carbon layer is also prepared through the carbonization of

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Figure 5. Synthetic route of SNBT organic compound.

dopamine precursor. CeO2 hollow structure not only allows the yellowish product was obtained. Yield: 0.82 g (87%). 1H NMR (400 MHz,
high organic compound loading and alleviates the structural DMSO-d6): δ 7.84–7.78 (m, 4H), 7.44 (d, J = 8.4, 2H), 5.31 (t, J = 5.7, 2H),
4.65 (d, J = 5.7, 4H); 13C NMR (100 MHz, DMSO-d6): δ 139.73, 132.08,
strains during repeated Li+ insertion/deinsertion processes, 127.47, 125.40, 124.23, 63.05; IR vmax (25 °C): 3214, 2867, 1399, 1209, 1127,
but also offers additional capacity. To take advantage of both 1017, 994, 979, 958, 907, 894, 820, 754, 706, 676 cm−1.
electrode materials, SNBT as the main active material bonds Synthesis of 2,6-Bis(bromomethyl)naphthalene: PBr3 (0.82 g, 3 mmol)
to CeO2@Carbon by the strong chemical bond with sulfur, was slowly added to a suspension of naphthalene-2,6-diyldimethanol
oxygen, and cerium atoms. As a result, the formed composite (0.57 g, 3 mmol) in freshly distilled DCM/DMF (v/v, 3:1, 16 mL). The
electrode (CeO2@Carbon/SNBT) exhibits high capacity reten- reaction was stirred in the ice-bath for 3 h, and then distilled water
(16 mL) was added to the mixture. The aqueous layer was extracted with
tion (75.2%) after 120 cycles and excellent rate capability. The
dichloromethane (16 mL × 3). The combined organic layer was dried
capacitive capacity and diffusion-controlled capacity are quan- over anhydrous Na2SO4, filtered through filter paper and concentrated
titatively analyzed by the detailed voltammetric investigation by reduced pressure. The rude product was purified by recrystallization
and supplemented by the exploration of EIS at different depths in ethyl acetate. Yield: 0.73 g (78%). 1H NMR (400 MHz, CDCl3): δ 7.81
of discharge. The results demonstrate that the strong chemical (d, J = 8.4, 4H), 7.53 (d, J = 8.3, 2H), 4.66 (s, 4H); 13C NMR (100 MHz,
bond and physical absorption of CeO2 in CeO2@Carbon/SNBT CDCl3): δ 136.06, 132.97, 128.97, 127.83, 127.60, 33.94; IR vmax (25 °C):
1505, 1436, 1228, 1205, 1160, 1128, 972, 944, 894, 864, 827, 701, 666 cm−1.
electrode could effectively block the lithiated SNBT material
Synthesis of Sodium Naphthalene-2,6-bis(carbodithioate): Sodium
within the electrode region. As expected, CeO2@Carbon/SNBT (0.19 g, 8 mmol) and sulfur powder (0.26 g, 8 mmol) were dissolved in
electrode shows much faster Li+ ions and electron transfer than dry methanol (50 mL). This mixture was heated to reflux for 4 h under
SNBT electrode. This strategy would provide a new perspec- argon in a two-necked flask equipped with a reflux condenser. Then,
tive for the rational and delicate design of rechargeable organic 2,6-bis(bromomethyl)naphthalene (0.63 g, 2 mmol) was added to the
lithium ion battery system. reaction mixture in small portions over a period of 1 h. The reaction was
allowed to reflux for additional 15 h, generating a red solution with some
solids suspended. After the solution was cooled at room temperature,
methanol was removed under reduced pressure. The dark red solid was
4. Experimental Section re-dissolved in THF (20 mL), and then the solution was filtered. Hexane
(15 mL) was added to the filtrate, and cooled to −15 °C. The precipitation
Sodium naphthalene-2,6-bis(carbodithioate) (SNBT) was synthesized was collected by filtration to yield the product, denoted as SNBT. Yield:
by three-step reactions from commercial materials (Figure 5), according 0.42 g (65%).1H NMR (400 MHz, DMSO-d6): δ8.54 (s, 2H), 8.32 (d, J =
to the reported methods.[6,29] The hybrid electrode materials (CeO2@ 8.5, 2H), 7.64 (d, J = 8.5, 2H); 13C NMR (100 MHz, DMSO-d6): δ249.52,
Carbon/SNBT) were synthesized by assembling SNBT with CeO2@ 149.84, 131.89, 126.25, 125.98, 123.85; IR vmax (25 °C): 1600, 1153, 1118,
Carbon hollow spheres. 1049, 1012, 955, 897, 815, 765674 cm−1.
Synthesis of Naphthalene-2,6-diyldimethanol: Dimethylnaphthalene- Preparation of CeO2@Carbon Hollow Spheres: CeO2 hollow spheres
2,6-dicarboxylate (1.22 g, 5 mmol) was slowly added to a suspension were prepared according to a typical method. Then, 365 mg of CeO2
of LiAlH4 (0.38 g, 10 mmol) in freshly distilled tetrahydrofuran (THF, hollow spheres were dispersed in 65 mL Tris-buffer (pH: 8.5) under
20 mL). The reaction was stirred in an ice-bath for 30 min, and then ultrasonication for 30 min to form a uniform suspension. Subsequently,
warmed to room temperature for another 1 h. Finally, the reaction 65 mg of dopamine was added under vigorous stirring, and the mixture
mixture was heated to reflux for 24 h. The mixture was re-cooled to was stirred at 30 °C for 72 h. Afterward, the resulting composite was
room temperature and the reaction was quenched with methanol. The collected by centrifugation (8500 rpm), then washed several times with
solvent was evaporated under reduced pressure, HCl (1 m, 20 mL) was deionized water, and then dried at 50 °C for 12 h. The resulting sample
added and the aqueous layer was extracted with ethyl acetate (20 mL was heated to 150 °C for 1 h in a tubular furnace under Ar atmosphere
× 3). The combined organic layer was dried over anhydrous Na2SO4, at a rate of 3 °C min−1, and then further heated to 600 °C for 4 h with a
filtered through filter paper, and concentrated by reduced pressure. The heating rate of 5 °C min−1.

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