Iron and Nitrogen Co-Doped Mesoporous Carbon-Based Heterogeneous Catalysts for Selective Reduction of Nitroarenes

Article abstract of DOI:10.1002/adsc.201900467

A facile fabrication of Fe and N co-doped mesoporous carbon (MC), as an efficient heterogeneous catalyst for the highly selective reduction of nitroarenes, is described. The Fe and N co-doped MC nanosheets are easily synthesized via a hydrothermal reaction between citrate acid and magnesium citrate, followed by calcination in the presence of melamine and potassium ferrocyanide. The Fe?N complex provides a unique active site for the selective reduction of 1-chloro-4-nitrobenzene, leading to the production of (E)-1,2-bis(4-chlorophenyl)diazene with a selectivity of >96%, in <40 mins. Control experiments based on non-doped, N-doped, and Fe-doped MC nanosheets demonstrate that selectivity greatly depends on the catalyst active component type, and that non-doped MC significantly contributes to the high efficiencies observed in the selective synthesis of azoxy compound intermediates. A broad range of substrates, including extra-functional groups on the nitroarenes rings, were successfully converted to the corresponding azo compounds at mild conditions with high selectivity. (Figure presented.).

Full text of DOI:10.1002/adsc.201900467

Title: Iron and Nitrogen Co-doped Mesoporous Carbon-Based
Heterogeneous Catalysts for Selective Reduction of Nitroarenes
Authors: Jitao Wang, Xiaochun Yu, Chongyang Shi, Dajie LIn, Jun Li,
Huile Jin, Xian Chen, and Shun Wang
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900467
Link to VoR: http://dx.doi.org/10.1002/adsc.201900467

10.1002/adsc.201900467
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Iron and Nitrogen Co-doped Mesoporous Carbon-Based
Heterogeneous Catalysts for Selective Reduction of Nitroarenes
Jitao Wang, Xiaochun Yu,* Chongyang Shi, Dajie Lin, Jun Li, Huile Jin, Xian Chen,
and Shun Wang*
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang, China, 325035
*E-mail: xiaochunyu@wzu.edu.cn; shunwang@wzu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
compounds by selectively reducing nitroarenes.[14–18]
Abstract. A facile fabrication of Fe and N co-doped
mesoporous carbon (MC), as an efficient heterogeneous Corma and co-workers[14,15] reported a gold-catalyzed
catalyst for the highly selective reduction of nitroarenes, is
described. The Fe and N co-doped MC nanosheets are
easily synthesized via a hydrothermal reaction between
citrate acid and magnesium citrate, followed by calcination
in the presence of melamine and potassium ferrocyanide.
The Fe-N complex provides a unique active site for the
selective reduction of 1-chloro-4-nitrobenzene, leading to
the production of (E)-1,2-bis(4-chlorophenyl)diazene with
a selectivity of >96%, in <40 mins. Control experiments
based on non-doped, N-doped, and Fe-doped MC
nanosheets demonstrate that selectivity greatly depends on
the catalyst active component type, and that non-doped MC
significantly contributes to the high efficiencies observed in
the selective synthesis of azoxy compound intermediates. A
broad range of substrates, including extra-functional groups
on the nitroarenes rings, were successfully converted to the
corresponding azo compounds at mild conditions with high
selectivity.
synthesis of azo compounds through a two-step, one-
pot reaction, under a partial pressure of hydrogen and
oxygen. Zhu et al.[16] observed that in the presence of
Au/ZrO2, the catalyzed coupling of nitroarenes to the
corresponding azo compounds in isopropyl alcohol,
proceeded when illuminated with incandescent light
or ultraviolet light. Hu et al.[17] used a catalyst
comprising ultra-thin Pt nanowires to obtain azo
compounds derived from their nitro counterparts.
Although outstanding selectivity and yields have
been achieved via tuning the heterogeneous catalysts
and reaction conditions, the high cost of noble metal
catalysts is a clear drawback, which severely prevents
their industrialization.[10]
Recently, numerous non-noble metals[18–20] and
carbon materials[21] have been employed as catalysts
toward the selective reduction of nitroarenes that
exhibit excellent selectivity and conversion efficiency.
Such reports inspire the design of new, low-cost
catalysts for commercialization.
Keywords: Azo compounds; Azoxy compounds;
Heterogeneous catalysts; Iron and nitrogen co-doping;
Selective catalyzed reduction
Iron, as a cheap, less-toxic and earth-abundant
element would be considered as an ideal catalyst if
comparable selectivity and yields could be achieved.
Fe3O4,[22] iron,[23,24] and -Fe2O3-based catalysts,[25]
have previously been reported to demonstrate such
type of catalytic reduction. Azo compounds are
formed as important intermediates, especially in the
presence of -Fe2O3, which follows a hydrogen
transfer reaction pathway. Although azo compounds
are thermodynamically stable through resonance,
such compounds are inevitably converted to anilines
on the surface of -Fe2O3 catalysts in the presence of
hydrazine. However, challenges remain to design
effective iron-based catalysts with the desired
catalytic properties for the highly selective formation
of azo compounds, rather than complete reduction to
anilines.[22–25]
Aromatic azo compounds are widely used as raw
materials in the chemical, food and pharmaceutical
industries.[1–5] For example, azo compounds are
considered as promising candidates across a wide
range of applications as nonlinear optics,[6,7]
photoregulation
promoters,[10] photochemical reaction species[11] and
photo-mechanical Primary azo
switches.[12]
components,[8,9]
catalytic
compounds are generally produced by azo coupling
and the Mills reaction;[10,13] however, these general
synthetic methods present numerous disadvantages,
such as the requirement of excess amounts of
oxidants or reductants and explosive initiators, having
poor selectivity, and producing environmentally
noxious wastes.[10] Noble metals have recently been
used as heterogeneous catalysts as an improved and
alternative method to efficiently obtain azo
Herein, for the first time, we report Fe and N co-
doped mesoporous carbon materials (denoted as
NMC-Fe) as effective heterogeneous catalysts for the
selective catalytic reduction of nitroarenes that yield
1
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10.1002/adsc.201900467
Advanced Synthesis & Catalysis
azo compounds as the final and stable products,
rather than anilines。
The synthesis procedure of NMC-Fe is systematically
detailed in the experimental section, in which the
carbon precursor is prepared via a Mg-assisted
calcination process.[26] To obtain NMC-Fe, a mixture
comprising the carbon precursor, melamine and
potassium ferrocyanide, at a mass ratio of 1:1:1, was
subjected to calcination at 800 °C for 1 hr, under a
nitrogen atmosphere. N-doped mesoporous carbon
catalysts (denoted as NMC) and Fe-doped
mesoporous carbon (denoted as MC-Fe) were
prepared under the same conditions as that of NMC-
Fe, except that no potassium ferrocyanide or
melamine was added, respectively.
As-synthesized Material Characterization.
A
vertically crosslinked 3D nanosheet morphology is
observed in the scanning electron microscopy (SEM)
and transmission electron microscopy (TEM) images
of NMC-Fe (Figure 1A–C), in which the (211) and
(121) planes of Fe3C are suggested to be
homogeneously dispersed. The nitrogen content in
NMC-Fe is calculated from x-ray photoelectron
spectroscopy (XPS), in Figure 1E, as 21.62 at.%. The
nitrogen adsorption/desorption isotherm of NMC-Fe
shows the carbon material to possess mesoporosity,
having a large specific surface area of 407.8 cm3 g−1
and mesopores with an average diameter of ~3.45 nm
(Figure 1F). The nanostructures of MC, NMC and
MC-Fe (Figures S1–S3) are similar, demonstrating
that the nitrogen and iron doping processes are not
influencing the intrinsic structure of the carbon
skeleton. To determine the binding energies of each
element in the MC, NMC and MC-Fe nanocatalysts,
XPS was performed, Figures S4–S6. Compared with
the MC-Fe catalyst (Figure S6), the Fe 2p XPS
spectrum of NMC-Fe (Figure 2) indicates a change in
the surface iron valence from Fe3+ to Fe2+. As a result
of nitrogen doping, the N 1s spectrum of NMC-Fe
shows that a large fraction of pyrrolic N is converted
to pyridinic N, which coordinates with Fe2+/Fe3+ to
form Fe-N complexes. Such Fe-N complexes have
been successfully applied in oxygen reduction
reactions for fuel cells.[27]
Figure 1. Characterization of Fe and N co-doped
mesoporous carbon materials (NMC-Fe) (the phase with
the highest degree of occupied active sites): (A) scanning
electron microscopy (SEM) image, (B) transmission
electron microscopy (TEM) image, (C) high resolution
TEM image, (D) energy-dispersive x-ray spectroscopy
mappings and spectrum, (E) x-ray photoelectron
spectroscopy (XPS) survey spectrum, and (F) nitrogen
adsorption/desorption isotherm (inset: pore size
distribution).
Figure 3. X-ray diffraction patterns of the as-obtained
mesoporous carbon (MC), and the N-doped MC (NMC),
Fe-doped MC (MC-Fe) and NMC-Fe catalysts.
Figure 2. XPS spectra of NMC-Fe: (A) C 1s, (B) N 1s, (C)
O 1s, and (D) Fe 2p regions.
2
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10.1002/adsc.201900467
Advanced Synthesis & Catalysis
The iron content in MC-Fe and NMC-Fe were
confirmed by x-ray diffraction (XRD) (Figure 3). For
iron-doped MC-Fe, the lattice structure attributed to
Fe3C can be detected. Conversely, for NMC-Fe, in
the presence of both iron and nitrogen, both the Fe3C
and Fe2O3 structures can be observed. Therefore,
nitrogen doping significantly influences the iron
valency and can promote the formation of the Fe-N
complex. Additionally, a MgO side product exists in
the nanocatalysts. Figure 4 shows the Raman spectra
of MC, NMC, MC-Fe and NMC-Fe. Of particular
note is the intensity ratio of the D band (~1350 cm−1)
to G band (~1590 cm−1), ID/IG, which determines the
relative concentration of local defects or disorders.
NMC-Fe exhibits a significantly smaller ID/IG ratio
when compared with the non-doped MC catalyst,
demonstrating that nitrogen and iron doping occupy
the vacancies and defect sites in the carbon
nanosheets. As a result, iron- and/or nitrogen-doped
carbon catalysts exhibit a smaller surface area than
the non-doped MC (as shown in Table S1).
excellent observed 3a selectivity of 96%, which for
the reduction of 1a, even outperforms noble metal
catalyst systems. Conversely, only a 3a selectivity of
21% is observed in the presence of the MC-Fe
catalyst system, highlighting the importance of the
co-doping of both Fe and N toward the selective
reduction of 1a. The NMC catalyst exhibits an even
lower 3a selectivity of 12%, confirming, once again,
that individually doping with iron or nitrogen yields
lower 3a selectivity as a result of the inability to form
the Fe-N complex.
Table 1. Catalyst influence on 1a conversion and product
yield.
Yieldb (%)
Cat.
(43mg)
MC
NMC
MC-Fe
NMC-Fe
-
Conv.
(%)
97
100
100
100
33
Entrya
2a
4
3a
4
4a
89
85
75
1
1
2
3
4
5
3
4
3
2
12
21
96
2
29
a) All reactions were conducted in the presence of 1-chloro-
4-nitrobenzene (1.0mmol) (1a), hydrazine hydrate (1.65
equiv.), KOH (1.5 mmol) and the corresponding catalyst
(43 mg) in toluene (1 mL), in a sealed 20 mL Schlenk tube,
b)
at 100 °C for 40 mins. Calculated according to the peak
area from GC-MS.
Typically, a hydrogen transfer mechanism is involved
in the iron-based catalyst systems.[22] The negatively
charged hydride adsorbents formed during the
transition are better stabilized by iron active centers
(electron-withdrawing substrates). The complexes
that are formed act as hydrogen transfer centers for
the selective reduction of nitroarenes to azo
compounds. To examine whether the NMC-Fe
catalytic conversion follows a traditional one-step
hydrogen transfer mechanism,[22] or a newly proposed
two-step, azoxy compound-mediated type of
catalysis,[17] the catalyzed-reduction of nitroarenes, in
the presence of NMC-Fe, was performed as a
function of temperature, as shown in Table 2.
Figure 4. Raman spectra of the as-obtained MC, NMC,
MC-Fe and NMC-Fe materials.
Selective Reduction of Nitroarenes. In Table 1, all
synthetic reactions were conducted in the presence of
1-chloro-4-nitrobenzene (1.0mmol) (1a), hydrazine
hydrate (1.65 equiv.), KOH (1.5 mmol), the
corresponding catalyst (43 mg), and toluene (1 mL),
sealed in a 20 mL Schlenk tube, at 100 °C for 1 hr.
The minimum amount of NMC-Fe catalyst, set at 43
mg, equates to 1.0 mmol 1a. Surprisingly, both Fe-
doped and N-doped carbon materials are able to
generate (E)-1,2-bis(4-chlorophenyl)diazene (3a)
from the reduction of 1,2-bis(4-chlorophenyl)diazene
oxide (4a), a key intermediate catalyzed by MC as an
essential pre-catalytic step. A low level of conversion
was observed for 1a in the absence of the above
carbon materials, suggesting that MC can be the
catalyst for 4a, while Fe and N co-doped MCs alter
the selectivity of this one-pot, two-step catalytic
reduction of 1a to 3a. Comparison of the chemical
compositions of the three carbon catalysts suggests
that the as-formed NMC-Fe is responsible for the
Scheme 1. Catalyzed reaction pathway as a function of
carbon catalyst composition.
The activation threshold of NMC-Fe is apparent at a
reaction temperature >40 °C. Below this critical
temperature, NMC-Fe remains inactive, yielding 4a
as the main product. The plausible reaction
3
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10.1002/adsc.201900467
Advanced Synthesis & Catalysis
Table 2. Influence of temperature and hydrazine hydrate concentration.
Sel. (%)b
NH2NH2·H2O
(equiv.)
Conv.
(%)
Entrya
T (°C)
2a
7
5
3
2
3
15
9
7
5
3a
90
94
85
70
49
84
91
93
91
69
46
4a
3
trace
12
28
48
trace
trace
trace
4
1
2
3
4
5
6
7
8
9
1.65
1.65
1.65
1.65
1.65
2.00
1.75
1.70
1.60
1.55
1.50
120
100
80
60
40
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
10
11
3
2
28
52
a)
All reactions were performed in the presence of 1a (1.0 mmol), hydrazine hydrate, KOH (1.5 mmol) and NMC-Fe (43
mg) in toluene (1 mL), in a sealed 20 mL Schlenk tube, for 1 hr. b) Calculated according to the peak area from GC-MS.
Figure 5. Reaction dynamics of the 1a-catalyzed reduction by: (A) MC, (B) NMC, (C) MC-Fe, (D) NMC-Fe materials. ■
-Conv%, ▼-4a, ▲-3a, ●-2a.
pathways are also confirmed by varying the
hydrazine hydrate concentration (Table 2). At a
relatively low concentration of hydrazine hydrate
(1.50 equiv.), selectivity is poor with 52% 4a
remaining in the system, likely as result of the active
sites not being fully occupied by hydrazine
adsorbents. Increasing the concentration of hydrazine
hydrate (to 1.55 equiv.) results in an additional 23%
conversion of 4a to 3a. The minimum requirement of
hydrazine hydrate (1.60 equiv.) must be exceeded to
ensure a high selectivity of 3a, for example, 91%.
Further
increasing
the
hydrazine
hydrate
concentration has a minimal effect on the selectivity
and yield of 3a. The reaction temperature has a
greater influence on the final product composition.
For example, aniline begins to emerge at 120 °C, as a
result of the decomposition of 4a. Overall, the
catalyzed-reaction pathway in the presence of NMC-
Fe appears to follow the two-step, azoxy compound-
mediated, one-pot selective reduction, as proposed in
Scheme 1.
Figure 5A–D shows that all four carbon catalysts
4
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10.1002/adsc.201900467
Advanced Synthesis & Catalysis
exhibit a high level of 4a production at a very initial
time-on-stream, ranging from 40% to 70%, strongly
indicating the catalytic role of the MC support. The
intrinsic zero-order reaction is also consistent with
the nature of the surface reaction on a catalyst.
Notably, Figure 5D reveals a ~96% 3a yield at a
reaction time of <40 mins. Table 3 and Table 4
demonstrate the general applicability of this MC-
based catalytic system, in which various nitroarenes,
especially for halide-containing substrates, were
selectively reduced to azo compounds or azoxy
compounds with good-to-excellent yields and
selectivity, respectively. Furthermore, aryl halides in
the meta and para positions can undergo nucleophilic
aromatic substitution reactions, further facilitating the
formation of azo compounds. H1-NMR, C13-NMR,
and GC-MS characterizations, together with
references to all studied azo compounds, are listed in
the Supporting Information.
Table 4. Mesoporous carbon (MC)-catalyzed reductive
coupling of nitroarenes to yield the corresponding
symmetric azoxy compounds.
Table 3. Fe and N co-doped mesoporous carbon (NMC-
Fe)-catalyzed reductive coupling of nitroarenes to yield the
corresponding symmetric azo compounds.
All reactions were performed in the presence of
nitroarenes (1.0 mmol), NH2NH2·H2O (1.65 equiv.), KOH
(1.5 equiv.) and MC (43 mg) in toluene (1 mL), in a sealed
20 mL Schlenk tube, at 100 °C for 1 hr. Values represent
isolated yields.
Figure 6. Recycling experiments for (A) NMC-Fe (43 mg)
and (B) MC (43 mg), 40 mins for each recycle. Reaction
conditions:
1-chloro-4-nitrobenzene
(1.0
mmol),
NH2NH2·H2O (1.65 mmol), KOH (1.5 mmol), toluene
(1mL), 100 °C, determined by GC. Magnetic separation of
NMC-Fe. NMC-Fe before (C) and after (D) magnetic
separation.
All reactions were performed in the presence of
nitroarenes (1.0 mmol), NH2NH2·H2O (1.65 equiv.), KOH
(1.5 equiv.) and NMC-Fe (43 mg) in toluene (1 mL), in a
sealed 20 mL Schlenk tube, at 100 °C for 1 hr. Values
represent isolated yields.
NMC-Fe catalyst can be recovered from the system
experiments after the reaction using magnets. The
results in Figure 6A show that a good conversion rate
and selectivity were maintained for the first three
recycles, however, after successive recycles thereafter,
the selectivity toward azo and azoxy compounds
reduced. According to Table S2, Figure 2D and
Catalyst recycling stability is an important factor to
evaluate the overall performance of heterogeneous
catalysts. NMC-Fe was subjected to continuous
operation to study the activity in a series of recycling
experiments. As shown in the Figure 6C–D, the
5
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10.1002/adsc.201900467
Advanced Synthesis & Catalysis
and magnesium citrate (0.02 mol) were dissolved in
20 mL double-distilled water, ultrasonicated for 10
mins, and thereafter, heated to 120 °C for 24 hrs, to
obtain yellow precipitates, which were subjected to
calcination in a horizontal tube furnace at 800 °C, at a
rate of 5 °C/min−1, under a nitrogen atmosphere for 1
hr. The resulting black composites were obtained and
denoted as the MC support.
Synthesis of NMC, MC-Fe and NMC-Fe. The
catalysts were all prepared using various
compositional mixtures containing the carbon
precursor, MC. For NMC, a MC melamine mixture
having a 1:1 wt.% ratio was used. A carbon precursor,
MC, and potassium ferrocyanide mixture having a
1:1 wt.% ratio was used for the preparation of MC-Fe.
A 1:1:1 wt.% ratio of MC, melamine and potassium
ferrocyanide was used for NMC-Fe. All mixtures
were subjected to heating at 800 °C for 1 hr.
General Synthetic Procedure for Azo Compounds.
Nitroarenes (1 mmol), hydrazine hydrate (1.65 mmol),
KOH (1.5 mmol), and the catalyst (NMC-Fe, 43 mg)
were mixed in toluene (1 mL), in a sealed 20 mL
Schlenk tube, under an air atmosphere, and stirred at
100 °C for 1 hr. The reaction progress was monitored
by TLC and/or GC-MS. After completion, the
product was purified by column chromatography
using ethyl acetate and petroleum ether as the eluents.
General Synthetic Procedure for Azoxy
Compounds. The synthetic procedure for the
formation of azoxy compounds followed that of the
azo compounds except for substitution of NMC-Fe
with MC.
Figure S8d, the reason for the decline in catalytic
activity after the recycling reactions is that the
proportion of surface iron in NMC-Fe decreases, with
a concomitant increase in the Fe2O3 content. Similar
recycling experiments were performed under
continuous operation to study the catalytic activity of
MC. The results in Figure 6B show that after
performing eight recycle experiments, a good
conversion rate and selectivity were maintained,
which indicated that the stability of MC was very
good.
In summary, novel Fe and N co-doped MC
materials are presented that demonstrate their
potential for the reduction of nitroarenes to azo
compounds, with a good-to-excellent yields and
selectivity. To the best of our knowledge, this is the
first example demonstrating that self-designed MCs
can function as an iron catalyst substrate, and act as a
catalyst for the selective synthesis of azoxy
compounds. The highest selectivity of 96% for the
conversion of azoxy compounds to azo compounds is
suggested to be related to the existence of the Fe-N
complex in the NMC-Fe catalyst. This cheap, fast and
efficient, two-step, one-pot catalytic process can be
used as a platform to provide a new synthetic method
for the selective production of azoarenes.
Experimental Section
General remarks all nitroarenes were purchased
from Aladdin. All reagents were used without further
purification. SEM was performed using a Nova 200
Nano instrument. TEM and high-resolution TEM
were performed using a JEOL-2100 instrument. XPS
was performed on a spectrometer from Kratos Axis
Ultradld, using mono AlKα (1486.71 eV) radiation, at
a power of 120 W (8 mA, 15 kV). XRD was
conducted on a Bruker D8 Advance diffractometer
using CuKα radiation (λ = 0.15406 nm), with the data
collected across a 2θ range of 20–80°. The Brunauer-
Emmett-Teller surface areas of the samples were
Acknowledgements
We are grateful for financial support from the National Natural
Science Foundation of China (51272182, 51772219, 21471116
and 51641210), the Zhejiang Provincial Natural Science
Foundation of China (LZ17E020002 and LZ15E020002), and the
Wenzhou Scientific and Technological In Public Project
(G20170018). We thank Jichang Wang, from University of
Windsor, and Edanz Group (www.edanzediting.com/ac) for
editing a draft of this manuscript.
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