A metal-organic framework-templated synthesis of γ-Fe2O3 nanoparticles encapsulated in porous carbon for efficient and chemoselective hydrogenation of nitro compounds

Article abstract of DOI:10.1039/c6cc00011h

The γ-Fe₂O₃ nanoparticles well dispersed in porous carbon were fabricated via a Fe-based metal-organic framework-templated pyrolysis. The resultant product exhibits excellent catalytic activity, chemoselectivity and magnetic recyclability for the hydrogenation of diverse nitro compounds under mild conditions.

Full text of DOI:10.1039/c6cc00011h

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Metal-Organic Framework-Templated Synthesis of γ-Fe O3
2
Nanoparticles Encapsulated in Porous Carbon for Efficient and
Received 00th January 20xx,
Accepted 00th January 20xx
Chemoselective Hydrogenation of Nitro compounds†
‡
‡
DOI: 10.1039/x0xx00000x
Yang Li , Yu-Xiao Zhou , Xiao Ma, and Hai-Long Jiang*
www.rsc.org/
5
The γ-Fe
2
O
3
nanoparticles well dispersed in porous carbon were drop in reaction solutions.
To obtain efficient and stable base metal-based catalysts,
fabricated via a Fe-based metal-organic framework-templated
pyrolysis. The resultant product exhibits excellent catalytic the encapsulation of highly dispersed metal/metal oxide
activity, chemoselectivity and magnetic recyclability for the nanoparticles (NPs) inside the porous host materials would be
hydrogenation of diverse nitro compounds under mild conditions.
an effective solution. In this context, metal-organic
6
frameworks (MOFs), a class of crystalline porous materials
Aromatic amines, primarily prepared via the reduction of
aromatic nitro compounds, are important feedstocks and key
intermediates for the manufacture of dyes, pigments,
agrochemicals, herbicides, pharmaceuticals and fine
with diversified and tailorable structures, have been
demonstrated to be ideal templates/precursors to afford
uniform and small metal and/or metal oxide NPs distributed
7
throughout porous carbon matrix. Although the synthesis and
1
chemicals. Due to the growing environmental concern,
multifunctionalities of MOF-derived composites have been
extensively reported, their applications in catalysis were
7
relatively rare. Given that Fe-based nanocatalysts are
hydrazine hydrate (N
2
H
4
·H
2
O) should be a suitable reducing
as a byproduct
agent for this transformation, generating N
2
only, which minimizes the influence on the surrounding
environment and the purity of the resultant anilines. On the
other hand, although Raney Ni has been demonstrated to be
effective for the reduction of simple nitroarenes, the
hydrogenation for their functionalized substrates usually relies
on noble metal-based catalysts (for examples, Ru, Pt, and Pd,
abundant, eco-friendly, inexpensive and magnetically
recyclable, the Fe
nitroarenes are considered to be suitable candidates.
With these in mind, a representative Fe-based MOF,
2 3
O species active for hydrogenation of
5
c
8
Fe
in
3
O(FA)
3 2 2 3
(H O) (NO ) (called Fe-MIL-88A, FA = fumaric acid),
a
spindle shape was synthesized. The Fe-MIL-88A
2
etc.). The high price and scarcity of these precious metals
microcrystals as templates/precursors were converted to
magnetic γ-Fe nanoparticles (NPs) embedded in porous
greatly limit their large-scale industrial applications. Moreover,
the presence of other reducible functional groups on the
nitroarenes makes the selective reduction especially for a nitro
group quite challenging. In addition to the supported Au
2 3
O
carbon via one-step facile pyrolysis at 500 °C. The resultant
product was found to be highly efficient, chemoselective and
magnetically recyclable for the hydrogenation of various nitro
compounds to anilines under mild conditions using hydrazine
hydrate as reductant (Scheme 1). To the best of our
knowledge, this is the first work on the transfer hydrogenation
of nitro compounds over MOF-derived nanocomposites.
3
nanocatalysts, most of precious metals are usually not
chemoselective; the modification of suitable additives to the
catalysts allows the improvement of the selectivity, while that
requires additional synthetic treatments and the additives also
4
cause environmental issues. As an alternative choice, the
heterogeneous catalysts based on base metals (for examples,
Fe, Co, and Ni), are earth-abundant and cost-effective, while
their leaching and sintering readily cause irreversible activity
3 3
Fe(NO )
Solvothermal
Method
+
Pyrolysis
FeꢀMILꢀ88A
Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key
Laboratory of Soft Matter Chemistry, Collaborative Innovation Center of Suzhou
Nano Science and Technology, Department of Chemistry, University of Science
and Technology of China, Hefei, Anhui 230026, P. R. China
Email: jianglab@ustc.edu.cn
γꢀFe
2
O
3
NPs@C
N H —H O
2
4
2
Nitro
Compounds
Anilines
†
Electronic Supplementary Information (ESI) available: Detailed Experimental
procedures and supporting figures. See DOI: 10.1039/x0xx00000x
These authors contributed equally to this work.
Scheme 1 Schematic illustration of the synthesis of porous carbon
encapsulated γ-Fe O NPs templated by Fe-MIL-88A.
2 3
‡
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active NPs, and also facilitate the transportation of catalytic
substrates and products.
The microstructure observation by scanning electron
microscope (SEM) suggests that Fe-MIL-88A microcrystals are
in a uniform spindle shape and length of ~700 nm (Fig. 1a).
After pyrolysis, taking Fe-500-1h as a representative, its shape
is almost retained while the size is reduced to some extent
(length: ~600 nm, Fig. 1b). A small number of spindles have
been broken, possibly caused by the rapid shrinking during
pyrolysis (Fig. 1b). As shown in transmission electron
microscope (TEM) image for Fe-500-1h, high-density small NPs
Fig. 1 Microstructure observation for Fe-MIL-88A and Fe-500-1h. (a) (6-10 nm) are uniformly distributed throughout the porous
SEM images of (a) Fe-MIL-88A and (b) Fe-500-1h. (c) TEM and (d)
HRTEM images of Fe-500-1h.
carbon (Fig. 1c, Fig. S4, ESI†). The high-resolution TEM
(
HRTEM) image displays clear lattice fringe, suggesting the
good crystallinity. The 0.25 nm interplanar crystal spacing is
corresponding to the (311) crystal plane of γ-Fe , further
inside the porous
The Fe-MIL-88A was solvothermally synthesized based on
8
Fe(NO ) ·9H O and fumaric acid in DMF solution. The
2 3
O
3
3
2
demonstrating the formation of γ-Fe
carbon (Fig. 1d).
2 3
O
structure of Fe-MIL-88A features a 3D network with hexagonal
channels composed by trimers of FeO6 octahedra linked by
fumarates. The phase purity of Fe-MIL-88A has been
confirmed by powder X-ray diffraction (XRD) (Fig. S1, ESI†). The
To further understand the existing form of Fe species, taking
Fe-500-1h as representative, its X-ray photoelectron
spectroscopy (XPS) has been investigated. As shown in Fig. S5
see ESI†), the Fe 2p exhibits two broad peaks at 723.9 and
10.3 eV, assigned to Fe 2p1/2 and Fe 2p3/2, respectively. Their
separation Δ = 2p1/2 - 2p3/2 = 13.6 eV are very similar to those
a
obtained Fe-MIL-88A samples were thermally treated at
o
different temperatures (from 500 to 700 C) in N atmosphere
(
2
7
to afford Fe-based NPs encapsulated inside porous carbon,
denoted as Fe-T-t (T and t represent pyrolysis temperature and
time, respectively; T = 500, 600, 700; t = 1 h, 2 h, 3 h). As
indicated by powder XRD patterns, the composition of the
products obtained at different temperatures displays distinct
differences (Fig. S2, ESI†). All peaks for Fe-500-1h can be
identified and indexed to the phase of maghemite (γ-Fe O ,
8c,10
reported for γ-Fe
powder XRD results above. Additionally, the characteristic
satellite peak at 719.6 eV for γ-Fe is also observable. All
2
O
3
,
which is also supported by the
2 3
O
these characterizations clearly suggest that the direct pyrolysis
o
of Fe-MIL-88A at 500 C leads to porous carbon incorporating
2
3
2 3
well-dispersed crystalline γ-Fe O NPs.
9
a
JCPDS NO. 39-1346), in which the broad peaks could be
caused by the small sizes of Fe O NPs. In contrast, the
We are now in a position to investigate the catalytic
performance of MOF-pyrolyzed Fe-T-t in the hydrogenation of
nitroarenes in the presence of hydrazine hydrate as reducing
agent. The nitrobenzene as the model substrate was first tried
to explore the optimized reaction conditions and also catalytic
activity of different catalysts (Table 1). Among different
2
3
diffraction peaks become much sharper in Fe-600-1h and
Fe-700-1h samples, revealing the presence of larger particles.
For Fe-600-1h, the strongest peaks can be indexed to α-Fe
(
JCPDS NO. 06-0696), while some relatively weak peaks are
9
b
assignable to γ-Fe O3 and Fe C (JCPDS NO. 35-0772). In
2
3
Fe-700-1h, α-Fe is still the major product, accompanying with
more portions of Fe C while no sign of γ-Fe O can be found. different catalysts.
Table
1 The catalytic reduction of nitrobenzene to aniline with
a
3
2 3
Moreover, the powder XRD patterns of Fe-500-2h and
Fe-500-3h give only α-Fe and Fe C, but do not contain γ-Fe O
3
2 3
species. These results unambiguously suggest the possible
reduction of Fe O to Fe or/and Fe C species at temperature
c
Entry
Catalyst
Fe-700-1h
Fe-600-1h
Fe-500-1h
Fe-500-2h
Fe-500-3h
Time (h)
Yield (%)
2
3
3
1
2
3
4
5
6
7
8
4
2
35.4%
36.9%
100
98.0
98.8
100
7.5
higher than 500 °C or with longer time of pyrolysis. Inductively
coupled plasma mass spectrometry (ICP-MS) results show that
the Fe contents are 21.99%, 25.99%, and 30.92%, respectively
for Fe-500-1h, Fe-600-1h and Fe-700-1h (Table S1), which is
1
1.5
2.5
3
understandable as some γ-Fe O have been reduced to α-Fe or
3
2
Fe C at higher temperatures, in agreement with powder XRD
3
2 3
γ-Fe O /C
results. The pore character and surface areas of pyrolysis
MIL-88A
no catalyst
Fe-500-1h
6
products were characterized by N sorption measurements at
2
12
12
0
77 K. They partially inherit the porosity of the MOF although
b
9
0
the samples obtained at different temperatures have distinct
sorption features (Fig. S3a, ESI†). The pore size distribution
a
Reaction conditions: 1 mmol nitrobenzene, 0.025 mmol Fe-based
o
analysis suggests that Fe-500-1h possesses hierarchical pores catalyst, 4 mmol hydrazine hydrate, and 5 mL alcohol, reflux at 85
C
b
c
(
Fig. S3b, ESI†), which would allow the exposure of active sites otherwise mentioned. Without hydrazine hydrate. Determined by
as far as possible, limit the migration and aggregation of the GC and using n-dodecane as standard.
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pyrolysis temperatures, the activity of the obtained catalysts Table 2 The catalytic hydrogenation of both aromatic and aliphatic
a
gradually decreases along with elevated pyrolysis nitro compounds to their amines with Fe-500-1h.
NO2
o
temperatures from 500 C to 700 C. As a result, the catalyst
o
NH2
Feꢀ500ꢀ1h
N H —H O
o
pyrolyzed at 500 C for 1h (Fe-500-1h) gives the best activity
2
4
2
R
R
(
entries 1-3). It seems that the prolonged pyrolysis time is also
not beneficial to the activity (entries 4-5). Therefore, it is safe
to conclude that γ-Fe as the component of Fe-500-1h is
more active than α-Fe or Fe C species obtained at higher
temperatures or longer time of pyrolysis. Despite this, the
γ-Fe species supported on active carbon is active but it
d
d
Entry
Substrate
Time (h)
1.5
Conv. (%)
Select. (%)
1
2
100
99
98
2 3
O
3
1.5
100
2
O
3
3
4
5
6
0.75
6
100
81
100
96.7%
>98
100
100
100
100
100
100
100
100
100
100
98
takes longer reaction time to achieve complete conversion
than that of Fe-500-1h (entry 6, Fig. S6, ESI†). As-synthesized
Fe-MIL-88A shows low activity in the reduction of
nitrobenzene to aniline (entry 7), and it is actually unstable in
the presence of hydrazine hydrate. In the absence of catalyst
or reducing agent (hydrazine hydrate), the hydrogenation of
nitrobenzene cannot proceed (entry 8-9). These results
suggest that the special structure of Fe-500-1h with
0.75
1.25
2
100
100
100
100
100
100
100
100
100
100
98
b
7
8
1.5
6
2 3
high-density active γ-Fe O sites well accessible to substrate
b
through the porous carbon matrix, could play crucial roles in
the high catalytic activity.
9
b
1
0
6
To demonstrate the stability and reusability of Fe-500-1h,
recycling experiments for the hydrogenation of nitrobenzene
were conducted. As shown in Fig. 2a, both catalytic activity
and chemoselectivity were very well remained in the ten
consecutive runs. TEM observation clearly demonstrated the
maintained NP size and shape of the catalyst after recycling
1
1
2
12
5
b
1
1
3
4
4
(Fig. S7, ESI†), suggesting its great stability and recyclability. To
b
1.5
2
verify the nature of the Fe-500-1h catalyst, the hot filtration
test was carried out from the mixture after 30 min of reaction,
no further conversion of nitrobenzene was observed even
after 2 hours of reaction under the identical conditions,
inferring that no leaching occurred to the catalyst and the
process should be truly heterogeneous (Fig. 2b). In addition,
the catalyst was easily separated by an external magnet due to
15
c
1
6
2
100
100
62
1
7
6
100
100
100
100
100
100
b
18
12
12
8
2 3
the strong magnetism of γ-Fe O (Fig. 2b, inset). Therefore,
b
1
9
69
Fe-500-1h catalyst presents an impressive catalytic activity and
recyclability, and possesses a truly heterogeneous catalytic
nature, showing potential application in chemical industry.
Encouraged by the superb performance of Fe-500-1h, a
variety of functionalized nitro compounds were investigated.
As shown in Table 2, most of the corresponding substituted
anilines were obtained with high conversion and selectivity.
Notably, halogen-substituted nitroarenes were effectively
2
0
100
100
81
2
2
1
2
1
2
a
Reaction conditions: 1 mmol substrate, 4 mmol hydrazine hydrate,
0.025 mmol catalyst,
mentioned. 5 mL CH
o
C
5
CN was substituted for alcohol. 5mL DMF was
mL alcohol, reflux at 85
otherwise
b
c
3
d
substituted for alcohol. Determined by GC using n-dodecane as
standard.
reduced to the corresponding haloaromatic amines without
obvious dehalogenation (entry 1-7). Furthermore, the high
performance was obtained in the hydrogenation of methyl-
substituted nitrobenzenes with 100% conversion and 100%
selectivity (entry 8-9). This catalyst also showed absolute
selectivity in the reduction of nitroarenes in the presence of
other functional groups, including amino, phenolic hydroxyl
and alcoholic hydroxyl, and no byproduct was detectable
Fig. 2 (a) Conversion (blue column) and selectivity (red column) of ten
consecutive runs and (b) hot filtration test of the reduction of
nitrobenzene with Fe-500-1h as
a catalyst. Inset of (b): The
(
entry 10-14). To our delight, the Fe-500-1h was also able to
photographs showing the facile separation of the catalyst by an
external magnet.
offer high chemoselectivity in the reduction of substituted
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nitroarenes with quite challenging reducible functional groups, Anhui Province (1408085MB23), the Recruitment Program of
including nitrile, aldehyde and ketone (entry 15-17), giving the Global Youth Experts and the Fundamental Research Funds for
only product of corresponding anilines while the reducible the Central Universities (WK2060190026).
functional groups were unchanged. This result further
2 3
highlights the chemoselectivity of this γ-Fe O -based
Notes and references
nanocatalyst, displaying remarkable advantage compared to
that of noble metal-based catalysts. Moreover, the
hydrogenation of heteroaromatic nitro compounds was also
investigated, among which although the reduction of
1
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2
2-chloro-3-nitropyridine and 2-hydroxy-5-nitropyridine were
(
&
relatively slow (62% and 69% conversion in 12 h, respectively),
the reaction selectivity for all substrates is as high as 100%
Organometallic Compounds (Wiley-VCH, ed. 2, Weinheim,
Germany, 2002).
(entry 18-20). In addition to the efficient and chemoselective
conversion for the reduction of substituted nitroarenes above,
we turned our interests to aliphatic nitro compounds (entry
3
4
5
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(
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2
1-22). In the presence of Fe-500-1h, aliphatic nitro
(
compounds were able to be reduced to the corresponding
aliphatic amines with high conversion, again manifesting that
the Fe-500-1h is effective for the hydrogenation of diverse
substrates, both aromatic and aliphatic nitro compounds.
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Based on the above results,
mechanism for the reduction of nitrobenzene catalyzed by
γ-Fe NPs encapsulated in porous carbon can be proposed
Scheme S1, ESI†). Nitrobenzene is firstly reduced to
nitrosobenzenze, and then rapidly converted to
a possible three-step
2
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O
3
7,
5
d
(
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phenylhydroxylamine. The two steps above possess fast
reaction kinetics. Finally, the intermediate transforms directly
to final product and this step is considered to be the
rate-determining step. Moreover, the Fe-500-1h catalyst
featuring hierarchical pores, as demonstrated by pore size
analysis (Fig. S3b, ESI†), might facilitate the transportation of
substrates, intermediates and products. In this case, diverse
functionalized nitro compounds can be reduced to the
corresponding amines under mild conditions.
6
7
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In summary, we have developed a highly efficient, low-cost,
2 3
and magnetically recyclable γ-Fe O @porous carbon
nanocatalyst for the hydrogenation of nitro compounds, via a
facile pyrolysis of a representative MOF, Fe-MIL-88A. The small
2 3
γ-Fe O NPs are well dispersed inside the porous carbon, which
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effectively limits the aggregation and growth of the
high-density NPs with an average size of ca. 6-10 nm and
facilitates the transportation of substrates, intermediates and
products. Remarkably, this non-noble metal oxide-based
nanocomposite behaves as efficient and stable catalyst for the
hydrogenation of a variety of substituted aromatic or aliphatic
nitro compounds, into their corresponding amines. More
importantly, in addition to the tolerance to general groups, the
catalyst exhibits high chemoselectivity to the reducible groups,
5
8
,
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2 3
including nitrile, aldehyde and ketone, etc. The γ-Fe O -based
nanocatalyst is readily recycled with an external magnet and
can be reused for at least 10 times without any loss of activity.
This study provides a versatile platform based on MOFs to
introduce active metal/metal oxide species highly dispersed
inside porous carbon matrix with targeted and improved
performance toward diverse catalytic reactions.
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This work is supported by the NSFC (21371162, 51301159
and 21521001), the 973 program (2014CB931803), NSF of
0
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