pubs.acs.

org/IC Article

Synthesis of a Magnetic 2D Co@NC-600 Material by Designing a

MOF Precursor for Efficient Catalytic Reduction of Water Pollutants
Dongsheng Wang, Fanming Zeng,* Xiaoli Hu,* Chun Li, and Zhongmin Su*
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ABSTRACT: 2D metal−organic framework (MOFs) can be ideal

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sacrificial templates for fabricating nanomaterials because of active

sites exposed on the surface rather than in pores and channels,
often exhibiting improved performance in catalysis applications. In
this study, the novel 2D layered cobalt-based MOF [Co(TPT)-
(fma)(H2O)2]·3H2O (Co-MOF) has been constructed by the
selection of high N atom content ligands. On this basis, a 2D
nitrogen-doped carbon-coated cobalt nanoparticle composite
(Co@NC) was prepared by using this MOF as a precursor.
Magnetic Co@NC has excellent catalytic activity and recycling
features regarding the reaction of 4-nitrophenol (4-NP) reducing
to 4-aminophenol (4-AP) in the presence of NaBH4 at ambient
temperature. 2D Co@NC-600 can reach nearly 100% conversion within 120 s and its stability remains almost unchanged after five
reaction cycles. Moreover, this Co@NC catalyst also is highly active for catalytic reduction of dyes such as Rhodamine B (RhB) and
Methylene blue (MB).

1. INTRODUCTION
In recent years, water pollution has been a huge environmental
challenge facing humanity. Nitrophenol and various dyes are
common organic pollutants found in industrial effluents.
Among them, 4-NP is the most difficult organic pollutant to
treat.1−3 Conventional water purification treatment cannot
effectively remove it because of it is highly water soluble. 4NP
has a strong irritating effect on the skin, which can inhibit the
central nervous system or damage liver and kidney functions
on entering the body.4−6 At present, a large number of physical
and chemical methods are used to remove pollutants in
wastewater, such as electrochemical degradation, photolysis,
adsorption, and catalysis.7−10 Reducing 4-NP to 4-AP is a good
way to deal with the pollution because 4-AP is a precursor
material for many industrial syntheses, such as picture
developers used in the dye industry, corrosion inhibitors, and
the manufacture of antipyretics and analgesics.11−13 With the
assistance of a catalyst, the reduction of 4-NP hydrogenation
directly to 4-AP through NaBH4 has received widespread
attention.14−17 Precious-metal catalysts which have excellent
catalytic effects such as Au, Ag, and Pd have been widely
reported for treating water pollutants, but they are extremely
rare and expensive, which have limited their applications in real
life.18−20 In the catalytic reduction of 4-NP, the most
important aspect is to find a non-precious-metal catalyst
which has high activity and recyclability. Transition metals, for
instance Fe, Co, and Ni, have been widely used in catalysis and
many other fields in recent years due to their low price and
good physicochemical properties.21,22 However, the transition-
metal particles can easily aggregate due to their high surface
energy, which reduces their activity. For these reasons, carbon-
based composite materials which have good mechanical and
chemical stability and electrical conductivity as a carrier of
metal particles have been extensively studied.23,24
MOFs have attracted more and more attention in different
fields, due to their adjustable hole structures and designable
frames.25−30 MOF-derived nanomaterials have been proven to
beideal sacrificial templates for the preparation of carbon
nanomaterials.31−34 They are usually prepared by pyrolyzing
the parent MOFs under an inert atmosphere in the absence of
other substances, for the reason that some important
advantages of MOFs can be retained in the derived
nanomaterials.35 Due to the periodic structure of the MOFs,
the active groups in the MOF-based carbon material are
uniformly dispersed in the nanomaterial. The structure and
morphology of the carbon material have also inherited those of
the parent MOF to a certain extent.36 Among them, cobalt-
and nitrogen-doped carbon-based materials synthesized by the
pyrolysis of various nitrogen-containing MOF precursors are
very promising catalysts. Lu et al. synthesized Co,N-CNF
Received: June 14, 2020
Published: August 11, 2020

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.inorgchem.0c01760

12672 Inorg. Chem. 2020, 59, 12672−12680
Inorganic Chemistry
products possessing outstanding ORR catalytic activity, whose
performance is superior to that of Pt/C at the same loading in
alkaline media.37 Yin et al. successfully obtained a Co SAs/N-C
species where the stabilization of Co SAs is strictly related to
the N-doped porous carbon support.38 Two-dimensional
catalysts have been a hot field of research in recent years
because the low-dimensional design of the catalyst can increase
the catalytic efficiency.39,40 2D nanocomposites derived from
2D MOFs have shown excellent performance in the field of
catalysis.41−43 Therefore, we designed and synthesized a novel
2D Co-containing MOF with a ligand containing N atoms and
used this Co-MOF as a sacrificial template for preparing
transition-metal nanocarbon materials. The design of MOF
precursors can be used to achieve microcontrol of the
properties of nanomaterials.
In this work, [Co(TPT)(fma)(H2O)2]·3H2O (TPT = 2,4,6-
tris(4-pyridyl)-1,3,5-triazine, fma = fumaric acid) was success-
fully synthesized under solvothermal conditions. The novel
Co-MOF was heat-treated under an N2 atmosphere to form
Co-carbon composites, denoted Co@NC. In the presence of
NaBH4, the prepared Co@NC has significant catalytic activity
for 4-NP and dye (RhB, MB) catalytic reduction in aqueous
solution. In addition, we conducted a series of experiments,
including the carbonization temperature for preparing the
catalyst, the effect of NaBH4 concentration, and the cycle
practicality of the catalyst, to comprehensively evaluate the
catalytic characteristics of the composite material.
2. EXPERIMENTAL SECTION
2.1. Materials. The chemicals and solvents used in this study were
of analytical grade and were purchased from commercial sources and
used without further purification: Co(NO3)2·6H2O, 2,4,6-tris(4-
pyridyl)-1,3,5-triazine (TPT), fumaric acid (fma), 4-nitrophenol (4-
NP), sodium borohydride (NaBH4), Rhodamine B (RhB), and
Methylene blue (MB) were purchased from Energy Chemical. N,N-
Dimethylformamide (DMF) was obtained from Sigma-Aldrich.
2.2. Instrumentation and Characterization. Single-crystal data
were collected on a Bruker Smart Apex II CCD X-ray diffractometer
at room temperature. Mo Kα radiation (λ = 0.71073 Å)
monochromated with a graphite monochromator was used as the
incident light source. The SHELXTL-97 program package was used
to analyze the crystal structure, and the obtained data were corrected
for absorption with the SADABS program. The morphologies of the
material were examined ny field-emission scanning electron
microscopy (FE-SEM) and transmission electron microscopy
(TEM). When an X-ray diffractometer (Bruker) was used to study
the crystal phase, the scanning range was 5−80° and the scanning
speed was 5°/ min. A Renishaw Model 2000 confocal microscope
Raman spectrometer was used to characterize the vibration character-
istics of the sample. The magnetic properties of the sample at 300 K
were determined on a superconducting quantum interferometer
magnetometer (SQUID). X-ray photoelectron spectroscopy (XPS)
was used to study the changes in the surface element composition and
chemical state. a Jasco V-770 spectrophotometer was used to obtain
UV spectral data.
2.3. Synthesis of the Novel 2D Co-MOF. A mixture of TPT
(15.6 mg, 0.05 mmol), fma (5.8 mg, 0.05 mmol), and Co(NO3)2·
6H2O (29.1 mg, 0.1 mmol) was dissolved in a mixed solution of 3 mL
of DMF and 3 mL of deionized water. The mixture was charged into a
polytetrafluoroethylene high-pressure reactor (15 mL) and placed at
100 °C for 3 days under autogenous pressure to react (Figure 1).
After the reaction was completed, the reaction kettle was naturally
cooled to room temperature to obtain yellow-brown block crystals.
The obtained crystalline products were washed three times with the
mother liquor and dried at room temperature before use. Anal. Calcd
for C22H24N6O9Co: C, 45.92; H, 4.20; N, 14.61. Found: C, 45.72; H,
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Figure 1. Schematic illustration for the synthesis of Co-MOF and the
highly efficient catalysis of Co@NC derived from Co-MOF.
4.00; N, 14.41. IR (KBr, cm−1): 426.33 (w), 882.08 (w), 1550.09 (w),
1861.06 (w), 1953.20 (w), 587.57 (m), 1151.92 (m), 1199.63 (m),
1313.16 (m), 511.88 (s), 640.22 (s), 681.35 (s), 798.17 (s), 974.22
(s), 1059.78 (s), 1374.04 (s), 1510.60 (s).
2.4. Synthesis of Co@NC. The synthesized Co-MOF was placed
in an alumina crucible that was then placed in a tube furnace for heat
treatment. As shown in Figure 1, under an N2 atmosphere, the
mixture was heated at a heating rate of 5 °C/min from room
temperature to T °C (T = 600, 700, 800) and was naturally cooled to
room temperature after being held for 2 h to obtain Co@NC-T
materials.
2.5. Reduction of 4-NP. A UV−vis spectrophotometer was used
to monitor the catalytic activity of the Co@NC catalyst. The catalytic
reduction of 4-NP was carried out in a quartz cuvette at room
temperature. First, 0.2 mL of a 2.5 mM solution of 4-NP and 2.5 mL
of deionized water were placed in the quartz cuvette, and then 0.2 mL
of a newly prepared NaBH4 solution (0.1, 0.2, and 0.3 M) was
dropped in. The solution quickly turned from light yellow to bright
yellow. Subsequently, 0.1 mL of a 1 mg/mL solution of the water-
dispersed complex where the catalyst homogeneously dispersed in
ultrapure water was dropped in. The absorbance of the solution was
measured at different times. The rate and progress of the reduction
reaction were monitored by recording UV−vis spectra at different
time intervals of the reaction system.
2.6. Reduction of RhB and MB. The catalytic reduction of RhB
and MB was also performed in a quartz cuvette, and the experimental
conditions of RhB and MB were the same as those for 4-NP. First, 10
mg of Co@NC-600 catalyst was dispersed in 25 mL of a 20 mg/L dye
solution and the mixture transferred into a cuvette. Then, 5 mL of 0.1
M NaBH4 was placed in the cuvette containing the system mixed
above, and the color of the mixed system quickly disappeared. Finally,
the progress of the reduction reaction was monitored by observing the
absorbance at the characteristic peak.
3. RESULTS AND DISCUSSION
3.1. Structure and Characterization of Co-MOF. An
analysis of single-crystal X-ray test data shows that Co-MOF
has a 2D structure and crystallizes in the monoclinic C/2c
space group. The molecular formula is [Co(TPT)(fma)-
(H2O)2]·3H2O (Co-MOF). The crystallographic parameters
of this compound are shown in Table S1. As shown in Figure
2a, the asymmetric unit of Co-MOF contains one Co atom,
two TPT ligands, two fma ligands, and two H2O molecules.
Each Co(II) adopts a six-coordinated coordination form,
which is coordinated with two oxygen atoms (O1) from two
carboxyl groups, two nitrogen atoms (N) from pyridine, and
two oxygen atoms (O2) from water (Co−O1 2.0513 Å, Co−N
2.196 Å, Co−O2 2.103 Å). The coordinated oxygen and
nitrogen atoms are derived from different ligands. These
ligands act as bridges, and the other end coordinates with other
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Figure 2. (a) Coordination environment of the Co(II) center. (b)

Stacked diagram of Co-MOF. (c) 2D network structure. (d)
Experimental and simulation XRD of Co-MOF.

cobalt ions, thus forming a 2D network structure. In the

stacked structure of the crystal, there is a π−π stack between
the paired TPT ligands whose surface to surface spacing is
around 4.402 Å; the distance between the layers is 7.210 Å,
which can also be called the distance between the nearest
adjacent Co atoms between the layers (Figure 2b). During the
self-assembly process of the crystal, the network structure is
reversed and superimposed. The uncoordinated pyridine group
Figure 3. SEM (a, b) and TEM (c) images of Co@NC-600. (d)
of the TPT ligand grows in the pores, reducing the porosity
High-resolution image of the Co@NC-600. (e) Elemental mapping of
and making the crystal structure more stable (Figure 2c). Co@NC-600.
The XRD pattern of the Co-MOF simulation coincided with
the experimental XRD pattern (Figure 2d), which confirmed molecules (H2O, O2, and CO2) in the air which was adsorbed
that the structural analysis was correct and the sample was high on the surface of the material.
in purity. TGA analysis under a nitrogen atmosphere was used 3.4. XRD and Raman Analysis. The XRD patterns of the
to study the thermal stability of Co-MOF. A mass loss of Co@NC material prepared by carbonizing Co-MOF at
approximately 10.9% is visible before 192 °C, which is mainly different temperatures are shown in Figure 4a. The materials
due to the removal of water molecules. The thermal
stabilization temperature of Co-MOF is about 340 °C. When
the temperature was increased from 340 to 390 °C, the weight
loss was about 22.5% due to the destruction of the compound
structure (Figure S1).
3.3. Micromorphology of Co@NC-600. The morphology
of the pyrolysis products of Co-MOF was studied by SEM and
TEM characterization. After Co-MOF was calcined under an
N2 atmosphere, cobalt ions form Co nanoparticles, and the
surrounding organic phase is converted into a nitrogen-doped
carbon skeleton which wraps the nanoparticles. It can be seen
from the SEM image that Co@NC-600 maintains a 2D layered Figure 4. XRD patterns (a) and Raman spectra (b) of Co@NC-T.
structure (Figure 3a), and Co particles can be seen on the
carbon surface (Figure 3b). The details of the internal show metallic Co (JCPDS no. 15-0806) and part of a weak
structure can be seen more intuitively from the TEM image CoO (JCPDS no. 01-1227) diffraction peak which is due to
(Figure 3c). The particle size of the Co particles is about 30− the surface Co nanoparticles of the sample exposed to the air
40 nm, and the Co nanoparticles in the carbon matrix are well and is caused by oxidation. In addition, as the calcination
dispersed without obvious agglomeration. High-resolution temperature is increased, the diffraction peak of Co becomes
TEM was used to further observe the microstructure of stronger. This is because the cobalt particles gradually
Co@NC. As shown in Figure 3d, the lattice fringes of metallic aggregate and detach from the carbon layer to be oxidized
Co particles and carbon can be clearly observed in Co@NC. while the temperature is increased.44 The Raman results show
The measured lattice plane distances are 0.20 and 0.34 nm, the structural difference of carbon during carbonization at
corresponding to the lattice plane (111) of Co and the lattice different temperatures (Figure 4b). The characteristic D band
plane (002) of graphitic carbon, respectively. The mapping (1339 cm−1) and G band (1586 cm−1) provide information
results show the distribution of C, Co, O, and N elements in about the disorder and crystallinity of carbon in the
the entire 2D material (Figure 3e). The C element content is composites, and their intensity ratio (IG/ID) is often used to
the largest, followed by that of the Co element. The O element judge the degree of graphitization in the carbon system. The
is attributed to C−O of fma and the oxygen-containing IG/ID ratio of all samples is approximate, indicating that the
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carbon is partially graphitized. As the carbonization temper-

ature is increased, the IG/ID ratio decreases slightly; Co@NC-
600 has the highest ratio, proving that its carbon crystallization
is relatively the best.
3.5. X-ray Photoelectron Spectroscopy. X-ray photo-
electron spectroscopy (XPS) was used to study the changes in
the surface element composition and the chemical state of
Co@NC. An XPS measurement spectral analysis (Figure 5a)

Figure 6. Magnetic hysteresis loop of Co@NC-600 at room

temperature (T = 300 K) and a digital photo of Co@NC-600
separated with a magnet in aqueous solution.

seen from Figure 7a that the absorption peak of pure 4-NP

appears at 317 nm. When only the Co@NC-600 catalyst is

Figure 5. XPS analysis of Co@NC: (a) full spectra of Co@NC-T; (b)

C 1s of Co@NC-600; (c) Co 2p of Co@NC-600; (d) N 1s of Co@
NC-600.

shows that the surface of Co@NC-600 mainly contains Co, C,

O, and N elements. Figure 5b shows the high-resolution C 1s
XPS spectrum, in which the peaks with binding energies of
284.7, 286.1, and 288.8 eV are assigned to the C−C, C−N,
and C−O bonds, respectively. The high-resolution Co 2p XPS
spectrum (Figure 5c) can be deconvoluted into two peaks
corresponding to metallic Co (777.7 eV) and Co−N (780.0
eV).45 The O peak mainly comes from the bare Co of the
sample surface being oxidized in the air. The high-resolution N
1s XPS spectrum (Figure 5d) shows characteristic peaks
centered at 398.3, 399.0, 400.6, and 402.2 eV, which belong to
pyridinic-N, Co-N, pyrrolic-N, and graphitic-N, respectively.46
3.6. Magnetic Properties. A superconducting quantum
interference device was used to study the magnetic properties
of Co@NC-600 in the range of −12500 to +12500 Oe at room
temperature. The test results are shown in Figure 6; the
hysteresis loop of Co@NC-600 exhibits superparamagnetic
behavior, which is caused by the contribution of Co
nanoparticles in the carbon skeleton and is a common feature Figure 7. (a) UV−vis spectra of 4-NP (black) and UV−vis spectra of
of ferromagnetic materials. The saturation magnetization value 4-NP + NaBH4 mixture (red). (b) UV−vis spectrum of mixture
system after adding Co@NC. UV−vis spectra of the 4-NP catalytic
of Co@NC-600 is 78.4 emu/g (T = 300 K), which indicates
reduction: (c) with the participation of Co@NC and NaBH4; (d)
that Co@NC-600 has good magnetic properties. As shown in with the participation of NaBH4 alone. (e) Relationship between time
the picture in the inset, the magnetic separation of Co@NC- and C/C0. (f) Comparison pictures before and after reduction.
600 was further tested with a magnet. Co@NC-600 responds
quickly to external magnetic fields and can be completely
separated in aqueous solution by a magnet. This feature greatly added, the catalytic reduction reaction cannot proceed, and the
facilitates recycling in actual use. 4-NP peak at 317 nm remains unchanged for 30 min (Figure
3.7. Catalytic Reduction of 4-NP. 4-NP is a common S2). After NaBH4 is added to the 4-NP solution, an absorption
environmental pollutant that is difficult to handle. Currently, peak appears at 400 nm and the solution changed from light
the most effective way to reduce 4-NP to 4-AP is by using a yellow to bright yellow. When a small amount of catalyst Co@
catalyst in the presence of NaBH4. We evaluated the catalytic NC was added to an aqueous solution containing 4-NP and
performance of Co@NC-600 by using this reaction. It can be NaBH4 at room temperature, a new absorption peak of 4-AP
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Inorganic Chemistry
ion appeared at 300 nm (Figure 7b). The absorption peak at
400 nm disappears completely, which indicates that 4-NP is
completely converted to 4-AP; the solution also changed from
bright yellow to colorless (Figure 7f). Therefore, we can
monitor the reduction and conversion process in real time
through UV−vis absorption spectroscopy. In the absence of a
catalyst, the peak at 400 nm remains unchanged after 30 min,
which indicates that the reduction of 4-NP did not occur
(Figure 7d). In contrast to this, when a small amount of Co@
NC catalyst was added to the reaction system, the reduction
reaction proceeded immediately. Co@NC-600 can completely
convert 4-NP to 4-AP within 120 s (Figure 7c), and the
conversion of 4-NP is almost close to 100% (Figure 7e). The
excellent catalytic performance of the Co@NC catalyst can be
attributed to (1) the doping of N atoms increases the number
of valence electrons and changes the charge environment of
carbon materials, improving the surface reactivity and
conductivity and (2) the 2D layered structure of the material
can expose more active sites and bring more active centers in
contact with the reaction system, which has an important role
in increasing the catalytic efficiency.
In this experiment, since the concentration of NaBH4 is
much higher than the concentration of 4-NP, pseudo-first-
order kinetics can be used to assess the rate constant of the
catalytic reduction, whose kinetics can be expressed as ln(Ct/
C0) = ln(At/A0) = −kt. Among them, C0 and Ct respectively
represent the concentration of 4-NP when the reaction system
is started and proceeds to time t; the ratio Ct/C0 can be
directly obtained from the corresponding absorbance ratio At/
A0 at 400 nm, and k and t are the apparent rate constant and
reaction time, respectively.
The carbonization temperature of the MOF precursor for
the synthesis of Co@NC is an important determinant of
catalytic performance. As shown in Figure 8a, the catalytic
Figure 8. Effect of (a) the carbonization temperature and (b) the
concentration of NaBH4 on the reaction of 4-NP.
activity of Co@NC-600 is better than those of Co@NC-700
and Co@NC-800. When the catalyst concentration was 1 mg/
mL, the time required for 4-NP to be fully catalytically reduced
was 120, 135, and 160 s (Figure S3), and the corresponding
linear correlation values k were calculated from the kinetic
formulas to be 0.0362, 0.0251, and 0.0224 s−1 for 600, 700, and
800 °C. It can be seen from the SEM and TEM photographs
(Figure S4) of different carbonization temperatures that, as the
temperature increases from 600 to 800 °C, the Co@NC
surface changes from flat to rough. When the carbonization
temperature is 600 °C, the particle size of the Co nanoparticles
is uniform. In the Co@NC-700 sample, the surface energy of
the Co particles is unstable, causing their agglomeration,
However, when the temperature is increased to 800 °C, Co
nanoparticles begin to agglomerate into large particles of over a
100 nanometers and break away from the carbon coating.47
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From an analysis of the high-resolution N 1s XPS spectra of
materials with different carbonization temperatures (Figure
S5), when the temperature is increased to 700 °C, the Co−N
peak disappears. At the same time, pyridinic-N, pyrrolic-N, and
graphitic-N peaks are enhanced. When the carbonization
temperature continues to increase to 800 °C, the peak of N 1s
almost disappears. The excellent catalytic activity of Co@NC-
600 can be attributed to the Co−N−C bond formed by the Co
element combined with the nitrogen atom of the carbon
skeleton. Co−N−C has been confirmed as the active center of
the catalytic reaction, and it drives the catalytic reaction
together with the Co-active site.48 Also, we tested the catalytic
performance of Co@NC-500, which has a lower carbonization
temperature. The reduction reaction completion time is 150 s,
and the reaction rate constant k is 0.0247 s−1, which are lower
than those of Co@NC-600 (Figure S6). This may be due to
the low degree of crystallization of Co nanoparticles in Co@
NC-500 and the carbon matrix around the Co nanoparticles is
unstable.51 The above results indicate that 600 °C is the
optimal carbonization temperature for preparing the catalyst.
The Co@NC-600 catalyst we designed has better performance
than the previously reported transition-metal catalyst and is
even comparable with that of the more active precious-metal
catalyst (Table S2).49−52
In addition, we explored the effect of NaBH4 concentration
on the rate of the catalytic reduction reaction (Figure 8b). In
order to determine the effect of NaBH4 concentration on the
reaction rate, we conducted a series of experiments by
changing the amount of NaBH4 with a constant amount of
4-NP and Co@NC. When the NaBH4 concentrations are 0.1,
0.2, and 0.3 M, respectively, the times required to complete the
reduction reaction are 190, 120, and 150 s (Figure S7) and the
corresponding k values are 0.0213, 0.0362, and 0.0288 s−1,
respectively. We know that the catalytic reduction reaction
mechanism of 4-NP is as follows: (1) BH4− ions in solution
contact the surface of the catalyst and transfer their electrons
to Co nanoparticles; (2) due to this, electron transfers form
hydrogen atoms which can attack nearby 4-NP; (3) Co
nanoparticles release electrons to the electron acceptor 4-NP,
transforming them to 4-AP.53,54 When the BH4− ions
concentration exceeds 0.2 M, the catalyst surface is already
saturated. Therefore, the reaction rate will not continue to
increase or even decrease. The results show that a
concentration of 0.2 M NaBH4 is the optimal concentration
for the reaction.
In the real processes, wastewater contains many compo-
nents; therefore, we used actual samples to test the anti-
interference of Co@NC-600. The experiment process is the
same; 2.5 mL of the actual sample was placed in the cuvette
instead of deionized water. The actual sample was taken from
Nanhu Lake, Changchun, Jilin, China, and the sample was
centrifuged for use. When the actual sample was added,
absorption peaks appeared at 317 and 400 nm together, which
is caused by the soluble ions in the actual sample. It can be
seen from Figure 9a that, in practical applications, Co@NC-
600 should be able to complete the 4-NP catalytic reduction
reaction in about 120 s; the reaction rate constant k is 0.0321
s−1 (Figure 9b), which is only a small decrease in comparison
to the theoretical experiment. The result shows Co@NC-600
has a certain anti-interference performance.
3.8. Reusability. When environmental and economic
factors are taken into account, the reusability of the catalyst
is an important evaluation criterion that affects its practical
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Inorganic Chemistry
Figure 9. (a) UV−vis spectra of the actual sample catalytic reduction.
(b) Relationship between time and ln(Ct/C0).
application. To determine the recyclability of Co@NC, five
repeated experiments were performed under the same
conditions. After each experiment, the catalyst in the reaction
system was separated with a magnet, washed, and dried for the
next experiment. Co@NC showed good performance in the
cycle experiments.
As shown in Figure 10a, in the four cycles of the reaction
that followed, the catalyst achieved nearly 100% complete
Figure 10. (a) Catalytic efficiency of Co@NC-600 for the reduction
of 4-NP. (b) Time required for each cycle of the experiment. SEM (c)
and XRD (d) after the fifth cycle.
reduction of 4-NP. However, with an increase in the number of
cycles, the time required for the complete reduction of 4-NP to
4-AP increased slightly (Figure 10b). In the first experiment,
the reduction reaction was completed at 120 s, and in the fifth
experiment, the time for complete conversion to 4-AP was
extended to 170 s. The reason for the increased reaction time
could be the loss of catalyst quality during separation and
washing, which leads to a reduction in catalytic efficiency.4,11
After five cycles, Co@NC-600 still maintains a 2D structure,
and the morphology did not change (Figure 10c). XRD after
the cycle showed the characteristics of Co (111), (200), and
(220) and C (002) peaks (Figure 10d), indicating that the
material did not undergo chemical changes before and after the
reaction.
3.9. Catalytic Reduction of RhB and MB. Dyes account
for a large proportion of common water pollutants, of which
RhB and MB are the most common. In order to verify the
universality of Co@NC catalytic performance, we further
applied its combination with NaBH4 in the application of dye
catalytic reduction. As shown in Figure 11a, the absorption
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Figure 11. Dynamic UV−vis spectra and digital photos of the
reduction of RhB (a) and MB (b) catalyzed by Co@NC annd
comparison of catalytic efficiency with and without catalyst in RhB (c)
and MB (d) solutions.
peak of the RhB solution appears at 553 nm. After 30 s of the
catalytic reduction reaction, the absorbance at 553 nm of the
reaction system almost disappears, only a very small peak can
be seen, and the solution becomes clear. Figure 11b shows the
change in the UV−vis absorption spectrum of the MB
reduction reaction. The maximum absorption peak of MB
appears at 663 nm. After less than 30 s of the reaction, the
characteristic peak of MB cannot be observed and the reaction
system quickly changes from blue to colorless. This
phenomenon indicated that the NN functional groups in
the organic dyes as the color group were reduced to N−N
(Figure 1).55,56 The conversion rate of the catalyst Co@NC-
600 on the dyes can be reflected as a function of C/C0 and t.
With an extension of the time, both RhB (Figure 11c) and MB
(Figure 11d) can achieve complete reduction conversion.
When the reaction time is 30 s, the conversion rates of RhB
and MB are 95.7% and 99.9%. There is almost no reaction in
RhB and MB solution without the catalyst (Figure S8). Thus,
the catalytic system which has high catalytic efficiency is also
suitable for the reduction treatment of dyes. Moreover, Co@
NC-600 still maintains an excellent catalytic effect in the
presence of multiple pollutants (Figure S9).
4. CONCLUSION
In summary, we used the N-containing ligands TPT and fma as
bridges to design and synthesize the novel 2D material
[Co(TPT)(fma)(H2O)2]·3H2O (Co-MOF). Layered mag-
netic Co@NC nanomaterials were successfully prepared by
applying Co-MOF as a template. Co particles are uniformly
dispersed in the N-doped carbon matrix. With the aid of
NaBH4, Co@NC has excellent activity and recycling ability for
the catalytic reduction of 4-NP in aqueous solution. The
experiments confirmed that the optimal carbonization temper-
ature for preparing the catalyst was 600 °C and the optimal
NaBH4 concentration was 0.2 M. The reaction can be
completed in 120 s with only 0.1 mg of the catalyst, which
still has a 100% catalytic effect in 5 cycles. The apparent rate
constant for the reaction of 4-NP reduction is 0.0362 s−1,
which is better than those of some precious-metal catalysts.
The excellent catalytic activity of Co@NC is due to the doping
of N atoms and the layered structure of the catalyst. The
https://dx.doi.org/10.1021/acs.inorgchem.0c01760
Inorg. Chem. 2020, 59, 12672−12680
Inorganic Chemistry
catalyst system also has a good effect on dye reduction. This
high-performance universal catalyst has great application
prospects in wastewater treatment.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c01760.
Crystal structure and physical characterization of Co-
MOF, physical characterization and additional catalytic
reduction experiments of Co@NC, and a comparison of
4-NP reduction rates of Co@NC with those of other
reported catalysts (PDF)
Accession Codes
CCDC 1992355 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_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
■
AUTHOR INFORMATION
Corresponding Authors
Fanming Zeng − School of Materials Science and Engineering,
Changchun University of Science and Technology, Changchun
130022, People’s Republic of China; Jilin Provincial Science and
Technology Innovation Center of Optical Materials and
Chemistry, Changchun 130022, People’s Republic of China;
orcid.org/0000-0002-3207-5141; Email: zengfm@
cust.edu.cn
Xiaoli Hu − School of Materials Science and Engineering,
Changchun University of Science and Technology, Changchun
130022, People’s Republic of China; Jilin Provincial Science and
Technology Innovation Center of Optical Materials and
Chemistry, Changchun 130022, People’s Republic of China;
Email: huxiaoli1113@cust.edu.cn
Zhongmin Su − School of Materials Science and Engineering,
Changchun University of Science and Technology, Changchun
130022, People’s Republic of China; Jilin Provincial Science and
Technology Innovation Center of Optical Materials and
Chemistry, Changchun 130022, People’s Republic of China;
Joint Sino-Russian Laboratory of Optical Materials and
Chemistry, Changchun 130022, People’s Republic of China;
orcid.org/0000-0002-3342-1966; Email: zmsu@
nenu.edu.cn
Authors
Dongsheng Wang − School of Materials Science and
Engineering, Changchun University of Science and Technology,
Changchun 130022, People’s Republic of China; Jilin Provincial
Science and Technology Innovation Center of Optical Materials
and Chemistry, Changchun 130022, People’s Republic of China
Chun Li − School of Materials Science and Engineering,
Changchun University of Science and Technology, Changchun
130022, People’s Republic of China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c01760
Funding
This work was financially supported by the National Natural
Science Foundation of China (21801021), Government
Funded Projects (61409220309, 6141B012822,
12678
pubs.acs.org/IC Article
6141B012823), the Science and Technology Development
Plan of Jilin Province (20180520150JH, 20180520170JH), and
the innovative Foundation of Changchun University of Science
and Technology (XJJLG-2017-02).
Notes
The authors declare no competing financial interest.
■
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