Highly efficient N-doped carbon supported FeSx-Fe2O3 catalyst for hydrogenation of nitroarenes via pyrolysis of sulfurized N,Fe-containing MOFs

Article abstract of DOI:10.1002/aoc.6294

Integrating MOFs as precursor, especially for employing N-containing organic linkers, with sulfides is an effective method to prepare the highly efficient N-doped carbon supported metal-based catalysts for hydrogenation of nitroarenes. In this work, a N,Fe-containing metal organic frameworks (MOFs; termed as MIL88-HMTA) with spindle-like structure was prepared via self-assembly method, in which hexamethylenetetramine (HMTA) linker was introduced as N source. Subsequently, N-doped carbon supported FeS_x-Fe₂O₃ catalyst (named FeS_x-Fe₂O₃@CN) was fabricated upon the pyrolysis of sulfurized MIL88-HMTA. Catalytic experiments reveal that the FeS_x-Fe₂O₃@CN delivered excellent performance for hydrogenation of nitroarenes in comparison with those of catalyst without sulfidation process (Fe₂O₃@CN) and conventional MIL88 derived catalyst (Fe₂O₃@C). The XRD, TEM, SEM/EDX, Raman, UV, and XPS analyses have revealed that the developed FeS_x-Fe₂O₃@CN catalyst exhibited outstanding catalytic efficiency was ascribed to synergistic effect between FeS_x and Fe₂O₃ species, abundant structural defects, more Fe-N_x species, and strengthened decomposition ability of hydrazine hydrate (N₂H₄?H₂O). Furthermore, the effect of sulfidation ratio (the mass ratio between thioacetamide and MIL88-HMTA) towards preparation of the developed FeS_x-Fe₂O₃@CN on the catalytic activity of hydrogenation reaction was also systematically performed. Notably, the optimized catalyst (denoted as FeS_x-Fe₂O₃@CN-8) exhibited unexpected performance and recyclability for hydrogenation of nitroarenes under mild condition. The pyrolysis of sulfurized N-containing MOFs may present a facile approach for fabricating MOFs-derived N-doped carbon supported catalysts, which provides a potential application in heterogeneous catalytic reactions.

Full text of DOI:10.1002/aoc.6294

Received: 19 March 2021
DOI: 10.1002/aoc.6294
Revised: 25 April 2021
Accepted: 3 May 2021
F U L L P A P E R
Highly efficient N-doped carbon supported FeS -Fe O
x
2 3
catalyst for hydrogenation of nitroarenes via pyrolysis of
sulfurized N,Fe-containing MOFs
1
1
1
1,2
1
Xuewei Li
| Wei She
| Jing Wang
| Weizuo Li
| Guangming Li
1
Key Laboratory of Functional Inorganic
Material Chemistry (MOE), School of
Chemistry and Materials Science,
Heilongjiang University, Harbin,
Heilongjiang, 150080, China
Integrating MOFs as precursor, especially for employing N-containing organic
linkers, with sulfides is an effective method to prepare the highly efficient
N-doped carbon supported metal-based catalysts for hydrogenation of
nitroarenes. In this work, a N,Fe-containing metal organic frameworks
(MOFs; termed as MIL88-HMTA) with spindle-like structure was prepared via
self-assembly method, in which hexamethylenetetramine (HMTA) linker was
2
School of Petrochemical Engineering,
Changzhou University, Changzhou,
Jiangsu, 213164, China
introduced as N source. Subsequently, N-doped carbon supported FeS -Fe O
2 3
Correspondence
x
Guangming Li, School of Chemistry and
Materials Science, Heilongjiang
University, Harbin, Heilongjiang 150080,
China.
catalyst (named FeS -Fe O @CN) was fabricated upon the pyrolysis of sulfu-
x 2 3
rized MIL88-HMTA. Catalytic experiments reveal that the FeS -Fe O @CN
x
2 3
delivered excellent performance for hydrogenation of nitroarenes in compari-
son with those of catalyst without sulfidation process (Fe O @CN) and con-
Email: gmli@hlju.edu.cn
2
3
ventional MIL88 derived catalyst (Fe O @C). The XRD, TEM, SEM/EDX,
2
3
Weizuo Li, School of Petrochemical
Engineering, Changzhou University,
Changzhou, Jiangsu, 213164, China.
Email: wzli@hlju.edu.cn;
Raman, UV, and XPS analyses have revealed that the developed FeS
Fe O @CN catalyst exhibited outstanding catalytic efficiency was ascribed to
-
x
2
3
synergistic effect between FeS and Fe O species, abundant structural defects,
x
2 3
wzli2006@126.com
more Fe-N species, and strengthened decomposition ability of hydrazine
x
Funding information
hydrate (N H ꢀH O). Furthermore, the effect of sulfidation ratio (the mass
2
4
2
the Reform and Development Fund
Project of Local University supported by
the Central Government; Heilongjiang
Provincial Government Postdoctoral
Science Foundation, Grant/Award
Number: LBH-Z17190; Doctoral Fund of
Ministry of Education of China, Grant/
Award Number: 2017M621315; Reform
and Development Fund Project of Local
University supported by the Central
Government
ratio between thioacetamide and MIL88-HMTA) towards preparation of the
developed FeS -Fe O @CN on the catalytic activity of hydrogenation reaction
x
2 3
was also systematically performed. Notably, the optimized catalyst (denoted as
FeS -Fe O @CN-8) exhibited unexpected performance and recyclability for
x
2 3
hydrogenation of nitroarenes under mild condition. The pyrolysis of sulfurized
N-containing MOFs may present a facile approach for fabricating MOFs-
derived N-doped carbon supported catalysts, which provides a potential
application in heterogeneous catalytic reactions.
K E Y W O R D S
x 2 3
FeS -Fe O catalysts, hydrogenation of nitroarenes, N,Fe-containing MOFs, N-doped
carbon, sulfidation
Appl Organomet Chem. 2021;e6294.
wileyonlinelibrary.com/journal/aoc
© 2021 John Wiley & Sons, Ltd.
1 of 13
https://doi.org/10.1002/aoc.6294

2
of 13
LI ET AL.
1
| INTRODUCTION
morphology as self-templating precursor, prepared with
Fe (NO ) ꢀ9H O, fumaric acid (FMA), and hexamethy-
3
3
2
Catalytic hydrogenation, one of outmost important reac-
tions in organic synthesis, is normally employed in the
preparation of commercial applications of numerous
products. Among hydrogenation products, arylamines
are valuable intermediates for production of dyes,
pharmaceuticals, pigments, and agricultural chemicals.
For hydrogenation process, the transition metal (Fe, Co, Ni,
etc.) catalysts,
been considered as ideal catalysts compared with noble-
metal (such as Pd, Pt, and Ru) catalysts
low cost and availability.
To date, the performance of N doped carbon catalysts
for catalytic reactions was greatly boosted due to the N
dopant could alter the wettability, Lewis basicity, and
lenetetramine (HMTA), where HMTA served as the N
donor, introduced into the frameworks of MIL88-HMTA
without using extra N source. Subsequently, FeSx-
Fe O @CN catalyst was fabricated via pyrolysis of the
2
3
sulfurized MIL88-HMTA. The developed FeSx-
Fe O @CN catalyst showed unexpected activity and
[
1–7]
2
3
selectivity for hydrogenation of nitroarenes by using
[8–17]
especially for Fe-based catalysts, have
N H ꢀH O as reductant on the basis of its abundant, low
2
4
2
[
49,50]
cost, and relatively safe (Scheme 1).
Extensive char-
[
18–33]
due to their
acterization techniques including XRD, FESEM, TEM
and HAADF-STEM, SEM/EDX, Raman, and XPS were
performed to investigate the origin of enhanced catalytic
performance of FeS -Fe O @CN catalyst for hydrogena-
x
2 3
tion of nitroarenes. This pyrolysis of sulfurized N,Fe-
containing MOFs may create a promising method for the
rational design of effective N doped carbon supported
non-noble metal-based catalysts in other heterogeneous
reaction.
[34–42]
electronic structure of carbon materials.
For the
hydrogenation of nitroarenes, the N dopant is favorable
for strengthening the interaction between acidic
nitroarenes molecules and carbon-nitrogen carrier by
dipole-dipole interaction, which is apt to promote the
absorption and/or activation of the nitroarenes. Until
now, the direct utilization of MOFs as suitable precur-
sors/templates for fabricating the structure-tailored
carbon hybrid materials without extra synthesis has
2 | EXPERIMENTAL
2.1 | Synthesis of MIL88-HMTA and
MIL88 MOFs
[
43–47]
become an increase tendency.
reported studies,
In previously
[48]
the Fe-MOFs (MIL88) as a subclass
of material has been extensively investigated on the basis
of its 3D topological structure, abundant carbon, and
high Fe content. In order to broaden its potential applica-
tions in heterogeneous reactions, it is highly desirable to
employ a tailored MIL88 MOFs (introducing the
N-functionalized linker) as the sacrificing precursor/tem-
plate to fabricate N-doped carbon supported Fe-based
catalyst.
The MIL88-HMTA was prepared as described previously
[
48]
with some modifications.
In a typical procedure,
0.36 mmol fumaric acid (FMA), 0.40 mmol Fe
(NO ) ꢀ9H O, and hexamethylenetetramine (HMTA)
3
3
2
were added together into the reactor. Subsequently,
ꢁ
the homogeneous solution stood at 110 C by
solvothermal method. After cooling down to room
temperature naturally, the precipitate was collected by
centrifugation and washed for several times and dried at
Herein, we present an N,Fe-containing MOFs
ꢁ
(MIL88-HMTA) as precursor to prepare highly efficient
80 C overnight.
FeS -Fe O catalyst for hydrogenation of nitroarenes to
arylamines via pyrolysis of sulfurized N,Fe-containing
MOFs. The developed MIL88-HMTA with spindle-like
The MIL88 was similar to that of MIL88-HMTA
except without choosing HMTA as the N-donor linker to
add into the mixed solution.
x
2 3
SCHEME 1 Schematic
illustration of preparing of the
x 2 3
FeS -Fe O @CN catalyst for
hydrogenation of nitroarenes to
functional arylamine

LI ET AL.
3 of 13
2
.2 | Synthesis of FeS -Fe O @CN-n
2.5 | Characterization
x
2 3
(
n = 3, 6, 8, and 10)
Powder X-ray diffraction (XRD) patterns were tested by a
Rigaku D/Max-3B X-ray diffractometer equipped with
a Cu Kα source (λ = 1.5406 Å). Field emission scanning
electron microscopy (FESEM) experiments were per-
formed by JEOLJSM-5600LV SEM/EDX instrument.
Transmission electron microscopy (TEM) and high-angle
annular dark field-scanning TEM (HAADF-STEM)
images were taken on JEM-F200 instrument coupled
with an element energy-dispersive X-ray spectrometer
(EDS) (200 kV). Fourier transform infrared (FT-IR) was
carried out on a Perkin-Elmer 100 spectrometer using
KBr pellets. Thermal analyses were determined in an alu-
The MIL88-HMTA was formed a homogeneous suspen-
sion by ultrasonication method. Then, various dosages
of thioacetamide at the different mass ratio (from 1:3 to
1
:10) with MIL88-HMTA were added, followed by
stirring vigorously for 1 h. Then, the solution was trans-
ferred into a Teflon-lined stainless-steel autoclave,
ꢁ
which was subsequently heated at 130 C. The final
product was separated, washed with water three times,
and dried in an oven. Then, a series of N-doped carbon
supported FeS -Fe O catalysts with different sulfidation
x
2 3
ratios were fabricated by pyrolyzing the sulfurized
ꢁ
ꢁ
ꢁ
MIL88-HMTA composites at 500 C. The resultant sam-
mina pan from 30 to 800 C at a heating rate of 10 C
ꢂ1
ples were denoted as FeS -Fe O @CN-n (n represents
min by STA-6000. The N adsorption-desorption mea-
x
2
3
2
the mass ratios of thioacetamide and MIL88-HMTA,
surements were recorded on a quantachrome autosorb
IQ and ASIQwin instrument at 77 K. The Raman data
were analyzed on a Thermo Scientific DXR Raman
microscope by using laser light of 532 nm wavelength to
characterize the graphitic nature of the carbon material.
The X-ray photoelectron spectroscopy (XPS) measure-
ments were employed by ESCALAB 250 XPS system. The
magnetic property of the prepared catalyst was measured
by Quantum Design SQUID MPMS-XL7 magnetometer
at 293 K.
n = 3, 6, 8, and 10). In addition, Fe O @CN and
2
3
Fe O @C catalysts were also synthesized by pyrolyzing
2
3
MIL88-HMTA and MIL88 MOFs under the same condi-
tion, respectively.
2
.3 | Catalytic performance tests for
hydrogenation of nitrobenzene
A mixture of nitrobenzene (0.81 mmol), N H ꢀH O
2
4
2
(3.2 mmol), catalyst (10 mg), and ethanol (10 ml)
were added into a 25 ml three-necked flask; then, the
whole equipment was purged three times with N2
to remove air. The resultant solution was heated to 85 C.
3 | RESULTS AND DISCUSSION
ꢁ
3.1 | Synthesis and structural
After cooling the reactor to room temperature naturally,
the catalyst was separated and washed with ethanol
for several times. The resulting solution was analyzed
by gas chromatography–mass spectrometry (GC-MS)
analysis.
characterization of MIL88-HMTA
The fabrication procedure towards N-containing
MIL88-HMTA precursor is depicted in Scheme 1. The
MIL88-HMTA was first successfully synthesized by a fea-
sible solvothermal method. The XRD analyses of the
resulting MIL88-HMTA and MIL88 showed high crystal-
linity and matched well with that of the reported MIL88
(Figure S1a). As shown in Figure S1b, it can be observed
2.4 | Catalytic decomposition of
hydrazine hydrate
2
ꢂ1
that the decreased specific surface area (309.3 m g
)
3
ꢂ1
The catalytic reaction was carried out in 50 ml round-
and total pore volume (0.31 cm g ) of MIL88-HMTA in
2
ꢂ1
bottom flask containing N H ꢀH O (3.2 mmol), catalyst
comparison with that of MIL88 (511.5 m
g
and
2
4
2
ꢁ
3
ꢂ1
(
10 mg), and ethanol (3 ml) at 85 C oil bath. Catalytic
0.39 cm g , respectively), which may be attributed to
the channel blocked by HMTA linker. The FT-IR analysis
further verifies the effect of HMTA linker on the struc-
ture of MIL88-HMTA (Figure S1c). The three characteris-
tic absorption peaks are attributable to the symmetric
and asymmetric vibration modes of COOH (1,594 and
decomposition reaction of N H ꢀH O, which releases of
2
4
2
H
(along with N ), was initiated by stirring the
2
2
mixture. The gaseous products during the reaction
were passed through a trap containing hydrochloric
acid (1.0 M) to ensure the absorption of NH . The
3
ꢂ1
ꢂ1
gas released was analyzed by a gravimetric water-
displacement method.
1,386 cm ) and N H/O H vibration (3,355 cm
)
towards MIL88, respectively. For spectrum of

4
of 13
LI ET AL.
ꢂ1
MIL88-HMTA, a new peak appeared at 1,255 cm
TG-DSC analysis (Figure S3) for MIL88-HMTA on
thermal property shows that an initial weight loss below
mainly originates from the C N stretching vibration of
HMTA linker. In addition, the obviously red-shift
ꢁ
110 C is assigned to the loss of physically adsorbed
ꢂ1
ꢁ
(
1,392 ! 1,386 cm ) for COOH stretching and the
water. And then the main weight loss above 287 C
increased intensity of the N H/O H in spectrum of
MIL88-HMTA as compared to that of MIL88 may be
formation of hydrogen bonding after introduction
of HMTA.
corresponds to the decomposition of the MIL88-HMTA
ꢁ
framework (279 C for MIL88). Moreover, for the DSC
profiles of MIL88-HMTA and MIL88, the characteristic
peak shifts to higher temperature for MIL88-HMTA
ꢁ
ꢁ
FESEM images of MIL88 (Figure S1d) and
MIL88-HMTA MOFs (Figure 1a) suggest that the pristine
MIL88 exhibits rod-shaped structure with an average size
of ꢃ5 μm in length and ꢃ2 μm in diameter. However, it
can be observed that MIL88-HMTA displays uniformly
distributed spindle-like morphology with a length of
ꢃ2 μm and a diameter of ꢃ0.4 μm. All of which indicate
that the introduction of HMTA has a significant effect on
the morphology and size of the MIL88-HMTA MOFs
during the synthesis process. The HAADF-STEM analysis
(312 C) in comparison with that of MIL88 (305 C),
indicating that the introduction of HMTA promotes the
thermal stability of MIL88-HMTA.
3.2 | Catalytic performance and
characterizations of as-synthesized
catalysts
The catalytic performance of three Fe-based catalysts
for hydrogenation of nitrobenzene to aniline was
investigated (Figure 2a). The developed FeS -Fe O @CN
(
Figure 1b) further confirms the existences of Fe, C, N,
and O elements from MIL88-HMTA. The uniformly
distribution of N element on the surface of MIL88-HMTA
suggests that the introduction of HMTA linker is
consistent with following SEM/EDX mapping analysis
x
2 3
catalyst exhibits the higher catalytic activity (69.6%) and
yield (69.5%) in comparison with those of Fe O @CN
2
3
(37.3% and 37.1%) and Fe O @C (16.5% and 16.1%). On
2
3
[
51,52]
(Figure S2).
the basis of previous reports,
the N dopant plays an
FIGURE 1 FESEM image (a),
HAADF-STEM image (b) of
MIL88-HMTA and the
corresponding mapping images
(
Fe, C, N, and O elements) (b1–b4),
and the EDS spectrum (c) as well as
surface content (d)

LI ET AL.
5 of 13
FIGURE 2 The catalytic
performance (a), the XRD
patterns (b), N
desorption isotherms (c), and
Raman spectra (d) of FeS
2
adsorption-
x
-
Fe
Fe
2
O
O
3
3
@CN, Fe
2 3
O @CN and
2
@C catalysts for
hydrogenation of nitrobenzene.
Reaction condition:
nnitrobenzene = 0.81 mmol,
nhydrazine hydrate = 3.2 mmol,
m
catalyst = 10 mg,
ꢁ
Vethanol = 10 ml, T = 85 C,
t = 1.0 h
TABLE 1 Physicochemical properties of FeS
x
-Fe
2
O
3
@CN,
FeS @CN (43.5% and 43.3%) exhibits higher conversion
x
Fe
2
O
3
@CN and Fe
2
O
3
@C catalysts
and yield for hydrogenation of nitrobenzene compared to
Fe O @CN (37.3% and 37.1%) under the same conditions.
a
b
c
2 3
S
BET
2
V
P
D
P
ꢂ1
3
ꢂ1
d
However, the catalytic activity of developed FeSx-
Fe O @CN (69.6% and 69.5%) for hydrogenation of nitro-
Catalyst
FeS -Fe
(m g
)
(cm g
0.35
)
(nm)
D G
I / I
2
3
x
2
O
3
@CN
56.8
2.4
0.89
0.72
0.85
benzene is highest among three Fe-based catalysts. In
Fe
Fe
2
2
O
3
3
@CN
@C
179.7
92.6
0.32
4.4
addition, for FeS @CN, the decomposition rate of
x
ꢂ1
O
0.14
4.4
N H ꢀH O is 3.2 μmol s (Figure S4a), which is lower
2
4
2
a
than that of developed FeS -Fe O @CN catalyst
x 2 3
S
BET is the specific surface area.
b
c
ꢂ1
V
P
is the total pore volume measured at P /P
0
= 0.99.
(3.9 μmolꢀs ). All of experiment results suggest that the
sulfidation could promote the catalytic performance of
FeS -Fe O @CN catalyst, which achieves unique syner-
D
P
is the most probable NLDFT pore size.
d
D G
I /I is the relative intensity ratio of D to G bands.
x
2 3
gistic effect between FeSx and Fe O3 species could
2
essential role on the charge mobility and electric
property. In hydrogenation of nitroarenes, the
decomposition experiments of N H ꢀH O (Figure S4a)
quickly activate N H ꢀH O to release H species and
2
4
2
further enhance the hydrogenation efficiency in reaction.
In general, the modified measurements (e.g., N modi-
fication and sulfidation) on the preparation of catalysts
have promotional effects on the absorption and/or activa-
tion of acidic nitroarenes molecules on the surface of
catalysts due to its unique electronic structure and Lewis
2
4
2
were conducted to verify the activated H species abilities
of FeS -Fe O @CN, Fe O @CN, and Fe O @C catalysts.
x
2
3
2
3
2 3
The experimental results have demonstrated that FeS -
x
ꢂ1
Fe O @CN catalyst (3.9 μmol s ) exhibits higher decom-
2
3
[
31,37,53]
position rate (denoted as DCHH) of N H ꢀH O than
basicity.
Herein, UV analysis was performed to
2
4
2
ꢂ1
those for Fe O @CN (2.8 μmol s ) and Fe O @C
2.5 μmol s ) under the same conditions (Table 1).
investigate the interaction between nitrobenzene and
as-prepared catalysts. As shown in Figure S5, the charac-
teristic absorption band corresponding to nitrobenzene
was observed at 259 nm. The desorption rate (denoted
2
3
2 3
ꢂ1
(
Furthermore, a comparative experiment was further
performed to investigate the effect of sulfidation towards
FeS -Fe O @CN catalyst on hydrogenation activity and
ꢂ3
ꢂ1
as DSNB) of Fe O @CN (8.8 ꢄ 10 μmol min ) changes
2 3
x
2
3
decomposed N H ꢀH O ability. As shown in Figure S4b,
significantly in contract to that of Fe O @C
2 3
2
4
2
ꢂ2
ꢂ1
for fully sulfurized catalyst (denoted as FeS @CN), the
(1.6 ꢄ 10
μmol min ) at regular time intervals
x

6
of 13
LI ET AL.
(
Table 1). However, the FeS -Fe O @CN exhibits the sig-
G bands, which refer to the defect degree of carbon
and the in-plane vibration of sp carbon atoms, respec-
tively. The relative intensity ratio of D band to G band
x
2 3
ꢂ3
ꢂ1
2
nificantly lower DSNB rate (4.5 ꢄ 10 μmol min ) than
those for other two catalysts, implying that the pyrolysis
of sulfurized N,Fe-containing MOFs method could
enhance the adsorption and/or activation ability of acidic
nitrobenzene molecules and further accelerate the
(I /I ) for the Fe O @CN (0.72) is obviously lower than
D
G
2 3
that of Fe O @C (0.85), suggesting that the incorporated
2
3
N species originated from HMTA linker could redistrib-
ute charge and promote the electron transfer between Fe-
based species and carbon-framework. However, for FeSx-
Fe O @CN catalyst, the I /I ratio is 0.89, which is obvi-
[
43]
reaction rate for hydrogenation of nitrobenzene.
In
addition, various characterizations have been proceeded
to examine the relationship between structure of FeSx-
Fe O @CN catalyst and catalytic performance for hydro-
2
3
D G
ous higher than that of Fe O @CN (0.72) catalyst, indi-
2
3
2 3
genation of nitroarenes.
cating that the pyrolysis of sulfurized N,Fe-containing
MOFs could increase the amounts of surface structural
Figure 2b exhibits XRD patterns of the as-prepared
FeS -Fe O @CN, Fe O @CN and Fe O @C catalysts.
defects
of
carbon
support.
The
generated
x
2
3
2
3
2 3
As shown in Figure 2b, the characteristic diffraction
peaks at 30.2 , 35.6 , 43.3 , 57.1 , and 62.9 can
be ascribed to the (220), (311), (400), (511), and (440)
surface structural defects could expose more active sites
and enhance mass transfer in the hydrogenation process.
The surface chemical bonding states of FeSx-
Fe O @CN, Fe O @CN, and Fe O @C catalysts were
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
planes of γ-Fe O3 (JCPDS No. 39-1346), respectively.
2
2
3
2
3
2 3
For Fe O @CN catalyst, the full width at half maxi-
elucidated by XPS analysis (Figure 3a–c). For Fe O @C,
2
3
2 3
mum of Fe O species becomes broader than that of
the deconvolution of Fe 2p can be divided into five
2
3
Fe O @C. This phenomenon indicates that the intro-
characteristic peaks. The peaks at approximately 723.9
2
3
2+
duction of the HMTA may improve the dispersity of
Fe O3 species. For pattern of FeS -Fe O @CN, new
and 710.7 eV are assigned to Fe , whereas 725.3
3
+
and 712.4 eV are attributed to Fe . The satellite peak
(718.7 eV) is consistent with the characteristic of
2
x
2 3
peaks corresponding to FeS (JCPDS No. 71-1680) and
2
[
3.
56]
Fe7S8 (JCPDS No. 71-0591) emerged, which suggests
that pyrolysis of sulfurized N,Fe-containing MOFs
γ-Fe O
In contrast to that of Fe O @C, the Fe 2p
2 3
2
XPS spectra of FeS -Fe O @CN and Fe O @CN catalysts
x
2
3
2 3
could generate the FeS species.
display a new peak at 710.2 eV corresponding to Fe coor-
x
[
57,58]
The pore characters and specific surface areas (SBET
)
dinated N to form Fe-N configuration,
which helps
x
of FeS -Fe O @CN, Fe O @CN, and Fe O @C catalysts
immobilize the metallic Fe atoms on their original posi-
tion and prevent their agglomeration and mobility.
Among three catalysts, the developed FeS -Fe O @CN
x
2
3
2
3
2 3
were evaluated by N adsorption-desorption analy-
2
[
54,55]
sis.
resulting carbon materials, based on the NLDFT
non-local density function theory) method, are listed in
Table 1. As shown in Figure 2c, Fe O @CN catalyst
The pore size distribution analyses (D ) of the
P
x
2 3
2
+
catalyst has the highest contents of Fe and Fe-N spe-
x
(
cies, suggesting that pyrolysis of sulfurized N,Fe-
2
+
containing MOFs could generate more active Fe
2
3
2
ꢂ1
presents higher SBET (179.7 m
volume (V ) (0.32 cm g ) than that of conventional
Fe O @C catalyst (92.6 m g and 0.14 cm g , respec-
g
) and larger pore
species and enhance the dispersity of Fe species. More-
over, from the S 2p XPS analysis (Figure 3d), it can be
3
ꢂ1
2
P
ꢂ1
3
ꢂ1
2ꢂ
2ꢂ
observed that the Sn and S (164.8, 163.9, 163.2, and
2
3
2
ꢂ
tively). For FeS -Fe O @CN catalyst, the S abruptly
BET
162 eV) as well as oxidized sulfur species (SOx ) (168.8
and 168.3 eV) species were formed on the surface
of developed FeS -Fe O @CN catalyst. Generally, the
x
2
3
2
ꢂ1
decreases to 56.8 m g , while the total pore volume
increases to 0.35 cm
3
ꢂ1
g . It can be observed that
x
2 3
FeS -Fe O @CN possesses the largest pore volume
degree of sulfidation plays a crucial impact on the
x
2 3
[
59]
among these three Fe-based catalysts, which may
strengthen the adsorption of nitrobenzene during the
hydrogenation process. Based on above analysis, it can be
observed that the SBET is not the main factor on the
catalytic efficiency of three catalysts for hydrogenation of
nitroarenes. Therefore, the following Raman and XPS
characterizations were performed to investigate the
difference in catalytic performance of three catalysts for
hydrogenation process.
preparation of the sulfurized catalysts.
Therefore,
the sulfidation ratios between thioacetamide and
MIL88-HMTA for synthesis of FeS -Fe O @CN catalyst
x
2 3
were optimized.
3.3 | Effect of sulfidation ratio
As shown in Figure 4a, the catalytic conversion of FeSx-
The structural changes and defects of three as-
synthesized catalysts were investigated by Raman
technique. As depicted in Figure 2d, two signal peaks at
around ꢃ1,375 and 1,587 cm correspond to the D and
Fe O @CN-3 for hydrogenation of nitrobenzene is 27.3%.
With the sulfidation ratio increases from 3 to 6, the cata-
2
3
lytic conversion and yield of FeS -Fe O @CN-6 increase
x
2 3
ꢂ1
from 27.3% to 49.5% and 27.1% to 49.3%, respectively.

LI ET AL.
7 of 13
FIGURE 3 Fe 2p XPS
x
spectra (a–c) for FeS -
Fe
2
O
3
2 3
@CN, Fe O @CN and
Fe
2
O
3
@C catalysts, and S 2p
XPS spectrum (d) for FeS
Fe @CN catalyst
x
-
2 3
O
FIGURE 4 Catalytic
activity (a), XRD patterns (b),
Raman spectra (c) of the FeS
Fe @CN-n (n = 3, 6, 8, and
0) catalysts, and Fe 2p XPS
spectrum for FeS -Fe @CN-
. Reaction condition:
x
-
2 3
O
1
x
2 3
O
8
n
n
nitrobenzene = 0.8 mmol,
hydrazine hydrate = 3.2 mmol,
catalyst = 10 mg,
ethanol = 10 ml, T = 85 C,
m
ꢁ
V
t = 40 min
Further increasing the sulfidation ratio, the catalytic
conversion (40.5%) and yield (40.3%) of FeSx-
conversion and yield of FeS -Fe O @CN-8 reached to
Fe O @CN-10 for hydrogenation reaction was detected
x
2
3
2 3
7
3.3% and 73.2%, respectively. Then, a decrease catalytic
when increasing the sulfidation ratio to 10. Therefore,

8
of 13
LI ET AL.
the differences in catalytic activities of four FeSx-
The structural changes and defects of the four
Fe O @CN-n (n = 3, 6, 8, and 10) catalysts for hydroge-
FeS -Fe O @CN-n (n = 3, 6, 8, and 10) catalysts were
2
3
x
2 3
nation of nitrobenzene to aniline have been elucidated by
various techniques including the following XRD,
SEM/EDX, TEM, Raman, and XPS.
evaluated by Raman experiment (Figure 4c). It can be
observed that the ratio values of I /IG for the four
D
FeS -Fe O @CN-n (n = 3, 6, 8, and 10) catalysts with
x
2 3
The crystalline structures of the as-prepared FeSx-
Fe O @CN-n (n = 3, 6, 8, and 10) catalysts with different
different sulfidation ratios are 1.1, 0.89, 0.86, and 1.1,
respectively. Obviously, the developed FeS -Fe O @CN-
2
3
x
2 3
sulfidation ratios were investigated by XRD analysis. As
8 catalyst exhibits the lowest I /IG ratio among
D
shown in Figure 4b, for FeS -Fe O @CN-3, the domi-
four catalysts, which endows FeS -Fe O @CN-8 with
x
2
3
x
2 3
nated γ-Fe O phase is identified by JCPDS file (JCPDS
No. 39-1346). Upon increasing the sulfidation ratio from
unique electronic configuration to facilitate the elec-
tron transfer and further accelerate the hydrogenation
rate in catalytic process.
2
3
3
to 6, the FeS (JCPDS No. 71-1680) and Fe S (JCPDS
2
7 8
No. 71-0591) species were generated in FeS -Fe O @CN-
The effect of the sulfidation ratios on the surface
chemical states of Fe and S elements for FeSx-
Fe O @CN-n (n = 6 and 8) catalysts was evaluated by
x
2 3
6
. Then, the ratio of FeS versus Fe S was improved
2 7 8
when the sulfidation ratio increased from 6 to 8. However,
the ratio of FeS versus Fe S obviously decreased for
2
3
XPS experiment (Figures 4d and S6). From the Fe
2
7 8
2+
2ꢂ
FeS -Fe O @CN-10 catalyst with the sulfidation ratio is
2p spectra, the Fe
and Sn
contents in FeSx-
x
2 3
1
0. Based on the above catalytic results, much more
Fe O @CN-8 (64.6% and 26.3%) are obviously higher
2
3
active FeS species contained in FeS -Fe O @CN-8 may
than those of FeS -Fe O @CN-6 (55.8% and 7.6%),
2
x
2
3
x
2 3
a
reason for why the FeS -Fe O @CN-8 delivers
indicating that more active FeS species were formed
x
2
3
2
the highest catalytic efficiency in hydrogenation of
nitrobenzene.
in FeS -Fe O @CN-8, which is well consistent with
above XRD analysis.
x
2 3
FIGURE 5 The TEM
a) and HRTEM (b) images, as
well as the HAADF-STEM
image of (c) the FeS
Fe @CN-8 catalyst and the
corresponding mapping images
S, O, and Fe elements) (c1–c3)
(
x
-
2 3
O
(
and the EDS result (d) (inset is
the values of elements)

LI ET AL.
9 of 13
a
TABLE 2 Hydrogenation of various substituted nitroarenes over FeS
x
-Fe
2
O
3
@CN-8 catalyst
Time
(h)
Yield
(%)
Selectivity
(%)
Entry
Substrate
Product
1
2.0
2.0
2.0
99.1
97.5
95.7
>99.9
2
3
>99.8
>99.9
[
b]
4
5.0
99.2
>99.7
5
6
2.0
2.0
99.8
99.7
>99.7
>99.9
7
8
1.0
5.0
99.6
99.7
>99.7
>99.8
[
b]
9
1
1
7.0
1.0
3.0
98.6
93.6
99.8
>99.7
>99.5
>99.9
[
b]
0
1
(
Continues)

10 of 13
LI ET AL.
TABLE 2 (Continued)
Time
(h)
Yield
(%)
Selectivity
(%)
Entry
Substrate
Product
1
2
8.0
96.8
>99.8
[
b]
1
3
4.0
99.2
>99.9
a
ꢁ
Reaction condition: substrate (0.8 mmol), hydrazine hydrate (3.2 mmol), catalyst (10 mg), ethanol (10 ml), 85 C.
b
Reaction condition: substrate (0.4 mmol), hydrazine hydrate (1.6 mmol).
The nanostructure of as-prepared FeS -Fe O @CN-8
catalyzed by FeS -Fe O @CN-8 under the optimized
x 2 3
x
2
3
catalyst was analyzed by TEM (Figure 5). As shown
Figure 5a, it can be observed that the sulfidation process
significantly affects the morphology of as-synthesized
FeS -Fe O @CN-8 catalyst. From Figure 5b, the five
reaction condition. The catalytic results are summarized
in Table 2; the FeS -Fe O @CN-8 catalyst exhibits high
x
2 3
activity (99.1%) and selectivity (>99.9%) (entry 1), which
is higher than other reported catalysts (Table S1). More-
over, the catalytic performance of FeS -Fe O @CN for
x
2 3
values of d- spacings were attributed to the (200) and
111) planes of FeS phases (0.274 and 0.312 nm, respec-
x
2 3
(
hydrogenation of nitrobenzene into aniline has also been
2
tively), (203) and (200) planes of Fe S phase (0.265 and
tested with H as reductant (Table S2). Meanwhile, it
7
8
2
0
.298 nm, respectively), and (220) plane of γ-Fe O phase
reveals that nitroarenes with electron-deficient groups
(containing chloro-, fluoro-, trifluomethyl-, ester-, and
cyano-, etc.) exhibited highly efficient yields and out-
standing selectivities to their corresponding arylamines
(Table 2, entries 2–10). Other substrates bearing electron-
rich groups including hydroxyl- and methyl- were fully
hydrogenated into corresponding arylamines (Table 2,
entries 11 and 12). The hydrogenation of multi-amino
nitroarene was also investigated (Table 2, entry 13).
Notably, all substituted nitroarenes exhibited activities
(>93.0%) and selectivities (>99%) without any products.
The above reaction results demonstrate that the
FeS -Fe O @CN-8 catalyst may serve as a promising
2
3
(0.255 nm), which is well in accordance with the above
XRD analysis. Meanwhile, distributions of Fe, S, and O
elements were investigated by HAADF-STEM and the
corresponding energy-dispersive X-ray (EDX) elemental
mapping analysis (Figure 5c). The representative
HAADF-STEM analysis of FeS -Fe O @CN-8 revealed
that Fe, S, and O elements were uniformly distributed on
the carbon-nitrogen support without any obvious aggre-
gation. Moreover, The SEM/EDX analysis was also per-
formed to investigate the distributions of C, N, O, S, and
Fe elements on surfaces of the FeS -Fe O @CN-n (n = 3,
x
2 3
x
2 3
6
, 8, and 10) catalysts. As depicted in Figure S7, the SEM
x
2 3
images of each catalyst and their corresponding EDX
mappings of overlay, C, N, S, O, and Fe coupled with
EDX spectra have also been conducted. From the EDX
mappings of Fe, O, and S elements coupled with Fe, O,
and S signals, it can be observed that FeS -Fe O @CN-8
candidate for hydrogenation of diverse nitroarenes to
their corresponding functionalized arylamines.
3.5 | Reusability of FeS -Fe O @CN-8
x
2
3
x
2 3
catalyst exhibits the most uniform distributions of Fe, O,
and S species among these four catalysts, which may
endow FeS -Fe O @CN-8 to deliver the highest catalytic
catalyst
Recyclability of catalysts is a significant criterion in the
heterogeneous reactions.
x
2 3
[
60–62]
performance in hydrogenation process.
Therefore, the reusability
of FeS -Fe O @CN-8 catalyst was investigated in
x
2 3
3
.4 | Hydrogenation of nitroarenes to
Figure 6. The magnetic property of FeS -Fe O @CN-8
x 2 3
substituted arylamines over FeSx-
Fe O @CN-8 catalyst
was measured by the Quantum Design SQUID MPMS-
XL7 magnetometer. As shown in Figure 6a, the magnetic
hysteresis loop for developed FeS -Fe O @CN-8 catalyst
2
3
x
2 3
ꢂ1
A wide variety of substituted nitroarenes were employed
as substrates for the hydrogenation to arylamines
exhibits a saturated magnetization of 10.4 emu g at
[
63,64]
5,500 Oe at 293 K.
As shown in Figure 6a inset, the

LI ET AL.
11 of 13
FIGURE 6 Hysteresis loop
(
a) and recyclability tests (b) for
FeS -Fe @CN-8 catalyst
x
2 3
O
FeS -Fe O @CN-8 catalyst could also be easily separated
and TGA of Fe-based catalysts, and the possible catalytic
mechanism.
x
2 3
by an external magnet and reused after thoroughly
washed with ethanol, further supporting above the mag-
[65]
netic analysis.
The recyclability test (Figure 6b)
ACKNOWLEDGMENTS
suggested that FeS -Fe O @CN-8 catalyst could be con-
This work was financially supported by the Reform and
Development Fund Project of Local University supported
by the Central Government, Doctoral Fund of Ministry of
Education of China (2017M621315), and Heilongjiang
Provincial Government Postdoctoral Science Foundation
(LBH-Z17190).
x
2 3
secutive reused for five times without obvious loss of
activity. Moreover, the possible catalytic mechanism over
FeS -Fe O @CN-8 for the hydrogenation of nitrobenzene
x
2 3
to aniline was given in the supporting information
Figure S8).
(
AUTHOR CONTRIBUTIONS
4
| CONCLUSIONS
Xuewei Li: Formal analysis; investigation. Wei She:
Software; validation. Jing Wang: Software; validation.
Weizuo Li: Conceptualization; project administration.
Guangming Li: Funding acquisition; resources.
The MIL88-HMTA was first synthesized by a feasible
solvothermal reaction between Fe
3
+
ion, FMA, and
N-containing HMTA organic linkers. A highly efficient
N-doped carbon supported FeS -Fe O catalyst (FeSx-
DATA AVAILABILITY STATEMENT
x
2 3
Fe O @CN) has been prepared via pyrolysis of sulfurized
Research data are not shared.
2
3
MIL88-HMTA. Integrating the unique properties of
MOFs and sulfides yields synergistic effect between FeSx
and Fe O , high dispersion of Fe species and content of
ORCID
2
3
Xuewei Li https://orcid.org/0000-0002-1455-7518
Wei She https://orcid.org/0000-0003-4513-0426
Jing Wang https://orcid.org/0000-0003-1082-0902
Weizuo Li https://orcid.org/0000-0001-6237-7581
Guangming Li https://orcid.org/0000-0001-6894-1550
2
+
Fe , and more structural defects in the carbon-nitrogen
framework, which accelerate adsorption and/or activa-
tion of reactant molecules (nitroarenes and N H ꢀH O)
2
4
2
during the hydrogenation process. All these unique
characters endow the developed FeS -Fe O @CN
x
2 3
catalyst exhibits unexpected hydrogenation activity and
selectivity for hydrogenation of nitroarenes in compari-
son with those of catalyst without sulfidation process
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How to cite this article: X. Li, W. She, J. Wang,
W. Li, G. Li, Appl Organomet Chem 2021, e6294.
https://doi.org/10.1002/aoc.6294
SUPPORTING INFORMATION
Additional supporting information may be found online
in the Supporting Information section at the end of this
article.