Nickel embedded in N-doped porous carbon for the hydrogenation of nitrobenzene to p-aminophenol in sulphuric acid

Article abstract of DOI:10.1039/c5cc06268c

An acid-resistant catalyst composed of nickel embedded in N-doped porous carbon is developed for the catalytic hydrogenation of nitrobenzene (NB) to p-aminophenol (PAP). The catalyst, due to a special electron donation from nickel to the N-doped porous carbon, shows an excellent catalytic performance and stability in sulphuric acid solution.

Full text of DOI:10.1039/c5cc06268c

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Nickel Embedded in N-Doped Porous Carbon for Hydrogenation of
Nitrobenzene to p-Aminophenol in Sulphuric Acid
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
b
a
a
a
Tao Wang, Zhen Dong, Teng Fu, Yanchao Zhao, Tian Wang, Yongzheng Wang, Yi Chen,
b
a
Baohang Han and Weiping Ding∗
DOI: 10.1039/x0xx00000x
www.rsc.org/
An acid-resistant catalyst composed of nickel embedded in N-
doped porous carbon is developed for the catalytic hydrogenation
of nitrobenzene (NB) to p-aminophenol (PAP). The catalyst, due to
a special electronic donation from nickel to the N-doped porous
carbon, shows an excellent catalytic performance and stability in
sulphuric acid solution.
p-Aminophenol (PAP) is an important intermediate for the
synthesis of pharmaceuticals such as acetaminophen,
dyestuffs and photographic chemicals. The one-pot synthesis
Scheme 1. The catalytic hydrogenation of NB to PAP.
of PAP from nitrobenzene (NB) is first reported by Henke and
1
Vaughen in 1940s.
The process involves catalytic
8
,9
for the hydrogenation of nitro compounds to anilines. It
shows that by receiving electrons from nickel, the CN would
become active for the adsorption and activation of hydrogen
while nickel is physically isolated from the reaction
environment by CN. Generally, CN could be prepared through
hydrogenation of nitrobenzene to intermediate product,
phenyl hydroxylamine (PHA) which then transforms into PAP
through acid-catalysed Bamberger rearrangement. At the
same time, PHA can also be further hydrogenated into aniline,
which is the main competing side reaction (Scheme 1). Later,
this technology was promoted by Benner for industrial
1
0
11
calcination of small molecules as cyanamide, melamine and
2,13
1
2
N-containing polymers as well.
Furthermore, porous
manufacture in 1968. Generally speaking, the process is
polymers have been considered to be an outstanding
candidate of the materials for supports of catalyst because of
usually catalysed by a supported precious metal catalyst such
−
3 5
as Pt or Pd.
However, the Bamberger rearrangement is
1
4,15
its high surface area and well-defined porosity.
Here we
realized under acidic condition such as sulphuric acid and
6
phosphoric acid, the loss of noble metal is inevitable. Given
report an efficient catalyst developed in one-step without any
additional supports or CN precursor by using an N-containing
porous polymer for substitution.
the high costs of noble metal catalyst, it makes sense to
develop an alternate with base metals which could still work
well for the reaction.
Glycoluril and terephthaldehyde are introduced to the
construction of an N-containing polymer (GTP) according to
1
our previous work and its possible structure is studied by
Although base metals such as Fe, Co, and Ni possess
catalytic activity for the hydrogenation of nitroarenes to
7
anilines, they could hardly survive from the strong acidic
6
1
3
Fourier transform infrared and solid-state C CP/MAS NMR
spectroscopy (Fig. S1, ESI†). The catalyst is obtained according
condition when simply supported on activated carbon, zeolite,
or silica. Thus catalysts with new structure should be
developed to prevent the metal from corrosion. Recently, N-
doped carbon (CN) prepared with underlying nickel is reported
1
7
to a method that is well reviewed by Qiao and Lu. The
process is achieved via dipping nickel nitrate solution into the
polymer followed by calcination at 873 K for 6 h with a heating
rate at 2 K min− in argon atmosphere (Scheme 2) and the
magnetic nanocomposite shows a good catalytic activity for
hydrogenation of NB to PAP and, moreover, the catalyst could
maintain its catalytic ability when pretreated at 393 K for ~100
h in 15 wt. % sulphuric acid solution, indicating an excellent
acidic stability.
1
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Fig. 2 XPS spectra of C 1s, N 1s and Ni 2p for Ni/CN. (The gray
lines in the spectra give the original data).
ascribed to N atoms bonded to carbon as a linkage in the form
1
9
Scheme 2. Process for the preparation of catalyst Ni/CN.
of H–N–(C)
2
which is in agreement with other’s results and
peak at 401.2 eV corresponds to graphic N according to the
2
0
The porous properties of GTP and the catalyst derived from research. Peaks in C 1s spectra are identified as CHx phase
2
1
2
GTP and nickel (Ni/CN) are studied by the nitrogen sorption (283.9 eV), graphitic sp -bonded amorphous carbon (284.6
2
2
isotherm measurements (Fig. S2, ESI†). As listed in Table 1, the eV), carbon atoms covalently bonded with nitrogen atoms in
2
3
two materials possess a comparative BET specific surface area an aromatic structure (285.3 eV) and carbon atoms in
2
−
1
24
(
SBET) about 550 m g . The Ni/CN shows a lower total pore carboxyl group (289.1 eV). As illustrated in Fig. 2, Ni 2p3/2 XPS
volume (Vtotal) than that of GTP due to the embedded nickel spectra of the catalyst with three main peaks appears at
particles. The morphological characteristics are elucidated by binding energy of 856.8 eV, 858.1 eV and 859.4 eV and several
SEM and TEM measurement and the images are exhibited in shake-up satellites at higher binding energy. The component at
2
5,26
Fig. 1. It could be seen in Fig. 1a that the obtained polymer is 856.8 eV corresponds to oxidized nickel state.
Peak located
composed of many small particles. As shown in Fig. 1b, nickel at 858.1 eV could be ascribed to oxidized state nickel in a
2
+ 27
). Interactions between Ni
2+
nanoparticles possess a well dispersity. Furthermore, the tetrahedral geometry (Ni
T
T
and
HRTEM image shows the metallic nickel crystalline particles support may result in the peak at 859.4 eV. The oxidized nickel
viewed from the [110] and [200] direction. The size of Ni state might be ascribed from strong interactions between
particles is approximately 9 nm which is in consistance with nickel and CN network by contributing electrons to CN, making
9
a
the result calculated from the (111) X-ray diffraction peak of Ni nickel electron-deficient
consistent with other reports.
and this phenomenon is in
2
7,28
laꢀce by using Scherrer equaꢁon (Fig. S3, ESI†).
Additionally, sulfur dopants
after calcination at 873 K contributed to p-toluenesulfonic acid
in the preparaꢁon of GTP (Fig S1a, ESI†) are detected as
9,30
2
oxidized sulfur, for instance, C
−SOx−C (Fig S4, ESI†).
Hydrogen/Deuterium (H D) exchange experiment focusing
−
on HD evolution rate with increasing temperature is conducted
to give information of the surface hydrogen. As shown in Fig.
3, for the sample of CN, derived from GTP, H-D exchange
begins at about 600 K is attributed to H specie α bonded to CN,
which is in agreement with the XPS result of C 1s (Fig. 2). And
Fig. 1 (a) SEM image of GTP; (b) TEM image of Ni/CN. (Inset of b
for Ni/CN, H
due to the presence of Ni. It is notable that a new signal at 518
originated from specie is detected, which is
−D exchange of α H begins at a lower temperature
is the HRTEM image .
K
H
β
Table 1 Porosity Properties of GTP and Ni/CN.
demonstrated to be the activated hydrogen for catalytic
hydrogenation of nitrobenzene according to the previous
2
−1 a
3
−1 b
c
Sample
S
BET (m g )
V
total (cm g )
Pore Size (nm)
9
a
report. Meanwhile, no peak at 410 K for chemisorbed
GTP
547
574
0.46
0.29
3.6
3.5
9
a
hydrogen on nickel itself is observed, indicating that Ni is
encapsulated by CN successfully.
Ni/CN
a
Surface area calculated from the nitrogen adsorption isotherm
using the BET method in the relative pressure (P/P ) range from
.05 to 0.2.
Since catalytic hydrogenation of nitrobenzene to p-
aminophenol is a reaction of multiple phases, involving an
organic phase of nitrobenzene, a solid catalyst, an aqueous
phase of sulphuric acid and a gas phase of hydrogen, the NB
conversion and PAP selectivity may depend on many factors
according to the procedure described in the previous
0
0
b
Total pore volume was calculated from nitrogen sorption
isotherms at P/P = 0.97.
0
c
Pore size was calculated by the BJH method.
3
literatures. And the reported catalyst performance of
In order to get more clear information about its structural
features, X-ray photoelectron spectroscopy (XPS) studies are
carried out (Fig. 2). Several peaks of N 1s spectra at 401.2 eV,
hydrogenation nitrobenzene is listed in Table S1 (ESI†). Here,
effects of acid concentration, hydrogen pressure, reaction
temperature and reaction time are discussed and the results
are displayed in Fig. 4. Figure 4a shows a NB conversion and
PAP selectivity vs temperature profile for the hydrogenation of
3
99.6 eV and 398.3 eV are displayed. The lowest binding-
1
energy peak is related to pyridinic N. The signal at 399.6 eV is
8
2
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Fig. 3 H−D exchange profiles of the samples and red lines are
the experimental data.
NB to PAP at a pressure of 1.0 MPa in a mixture of NB and 10
wt. % aqueous sulphuric acid. The selectivity to PAP would
decrease a little when the temperature higher than 403 K,
indicating that higher reaction temperature may benefit
further hydrogenation of phenyl hydroxylamine as an
intermediate product. When reaction time is extended to 3 h
Fig. 4 Effects of temperature (a), reaction time (b) hydrogen
2 4
pressure (c), and H SO concentration (d) on hydrogenation of
(Fig 4b), the nitrobenzene conversion increases from 8.0 % to
nitrobenzene to PAP
38.0 % with PAP selectivity changes little to 95.6 %, reflecting
the further hydrogenation of phenyl hydroxylamine into
6
aniline on the catalyst surface.
Considering that the reaction involves the hydrogenation of
nitrobenzene to PHA and aniline hydrogenated from PHA is a
major by-product, the effect of hydrogenation pressure on
catalyst activity and PAP selectivity is investigated at 393 K and
the reaction time is set for 1 h. As shown in Fig 4c, when
hydrogen pressure is increased from 0.5 to 2.0 MPa, the
conversion of nitrobenzene varies from 22.4 % to 34.1 %.
However, selectivity to PAP declines from 100 % to 90.5 %.
Since the acid-catalysed Bamberger rearrangement should
conduct in aqueous solution, the selectivity of the reaction
depends on whether PHA could desorb from the surface of the
catalyst and diffuse into the aqueous solution successfully. The
increase of hydrogen pressure would prevent desorption of
PHA from catalyst surface, leading to further hydrogenation of
Fig. 5 Recyclable catalytic hydrogenation of NB to PAP with
Ni/CN.
3
concentration of 15 wt. % is chosen as the optimum for the
catalytic reaction. Though Ni/CN does not show a high NB
PHA to aniline and a decreased PAP selectivity. Meanwhile,
with increasing hydrogen pressure, more surface hydrogen
would be absorbed on the active sites of the catalyst, which
would promote the both nitrobenzene hydrogenation to PHA
and its further hydrogenation to aniline, resulting in a higher
nitrobenzene conversion and a decrease in PAP selectivity.
Given that acid is essential for Bamberger rearrangement,
otherwise aniline is the only production, it is necessary to
evaluate the importance of acid concentration on PAP
selectivity. Aqueous sulphuric acid solution with different
concentration varied from 10 wt. % to 20 wt. % is used to
study its effects while other reaction conditions are kept
constant and the result is exhibited in Fig 4d. A continuous
increase of NB conversion from 28 % to 43 % without any
decrease in PAP selectivity is achieved with the increasement
of acid concentration. However, the NB conversion nearly
keeps constant for a higher sulphuric acid concentration,
3
1,32
conversion as some noble metal containing catalysts
due
to a high content of sulphur according to the XPS
measurement (Table S2, ESI†), while CN made from GTP
shows little catalytic activity, such a model of Ni embedded in
CN prepared from impregnation of nickel ion into N-containing
porous polymer is proved to be a candidate for catalytic
hydrogenation NB to PAP. Additionally, a recycle test for the
catalyst is carried out to investigate its service life. As shown in
Fig. 5, the catalyst still possesses about 70 % catalytic activity
of fresh catalyst when used for 5 times. The gradual decrease
in catalytic performance during recycling may be attributed to
absorbed organic substances due to the large specific surface
area and high adsorption ability of Ni/CN and this result is
3
3
similar to the report.
In order to get more details about the spent catalyst, XPS
tests are conducted. As listed in the Ni 2p3/2 core level spectra
3
c
which is in agreement with the other report. Hence, an acid
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(
Fig. S5, ESI†), three peaks located at 856.9 eV, 858.1 eV and
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slightly corrosion of nickel in reaction process when
considering the porous properties of Ni/CN. Moreover, Ni
8
9
content in H
2 4
SO solution with a constant volume (100.0 mL) is
Ding, Chin. J. Catal., 2015, 36, DOI: 10.1016/S1872-
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4
1
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×
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3, 22988.
1
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spectrometry (XRF) as 15.5 wt. % and 1.98 wt. % respectively
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7
.23 wt. % in Ni/CN when refers to the results of elemental 14 C.E. Chan-Thaw, A. Villa, P. Katekomol, D.S. Su, A. Thomas
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1
1
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2
2
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