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Key Laboratory of Soft Chemistry and Functional Materials, Nanjing University of Science and Technology, Ministry of Education, Nanjing 210094, China
Key Laboratory of Fine Petrochemical Engineering, Changzhou University, Changzhou 213164, China
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, Huaiyin Normal University, Huaian, Jiangsu 223300, China
a r t i c l e
i n f o
Article history:
Received 2 February 2015
Received in revised form 23 June 2015
Accepted 24 June 2015
Available online 30 June 2015
Keywords:
Nickel nanoparticles
Carbon black
Catalytic hydrogenation
Nitrophenols reduction
Lower temperatures
a b s t r a c t
A carbon black (CB) supported nano-Ni catalyst is prepared by a facile method using nickel chloride as the
nickel source and hydrazine hydrate as the reducing agent. TEM observation shows that Ni nanoparticles
have a good dispersion with a narrow size distribution on the surface of carbon black. The catalyst exhibits
signicantly high catalytic activity for hydrogenation of nitrophenols even at 30 C. The high performance
obtained here can be attributed to the specic characteristics of the nanostructure of the catalyst and
the synergistic effect of nano-Ni and carbon black, including plenty of oxygen-containing groups of carbon black for anchoring Ni atoms, strong adsorption ability for organic molecules and good conductivity
for electron transfer from the carbon black to Ni nanoparticles. Moreover, the Ni-based catalyst is relatively cheap and magnetically separable, thus achieving a low-cost hydrogenation of nitrophenols to
aminophenols.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Nitroaromatic compounds are being widely used in industrial
processes, including the manufacture of dyes, pharmaceuticals, pigments, pesticides, wood preservatives and rubber chemicals [14].
Therefore, nitroaromatic compounds are often presented as water
pollutants due to the release in industrial efuents. These pollutants pose signicant health risks due to their carcinogenicity and
may leave residues in animal products such as meat and eggs.
Among various nitroaromatic compounds, nitrophenols are listed
as one of top 114 organic pollutants by the United State Environmental Protection Agency (USEPA) [5,6], and especially, they have
been implicated in carcinogenesis, teratogenesis and mutagenesis
[57]. On the other hand, it is hardly inevitable that nitrophenols
are a kind of important byproducts for the synthesis of nitro compounds, such as nitrobenzene, which can be produced through
benzene nitration in the presence of mixed acid. Moreover, apart
from mono-nitrophenols, di- and tri-nitrophenols (DNP and TNP)
with stronger toxicity, carcinogenicity, mutagenicity and teratogenicity, are also signicant byproducts in industrial processes
[5,8,9]. Besides, the nitrophenols can also be produced in the air
Corresponding authors.
E-mail addresses: zll@hytc.edu.cn (L. Zhang), xqsun@cczu.edu.cn (X. Sun),
wangx@njust.edu.cn (X. Wang).
http://dx.doi.org/10.1016/j.apcatb.2015.06.043
0926-3373/ 2015 Elsevier B.V. All rights reserved.
409
410
Fig. 1. (ab) TEM images of Ni and Ni0.22 /CB catalysts; (c) High-resolution TEM image of Ni0.22 /CB catalyst; (d) Particle size distributions of nano Ni and Ni0.22 /CB catalysts.
411
Fig. 2. XRD patterns of Ni, Ni0.49 /CB, Ni0.22 /CB and Ni0.002 /CB catalysts.
metallic Ni, the most intense doublet (855.4 eV and 873.0 eV) is due
to Ni2+ in NiO and the second doublet (861.0 eV and 879.0 eV) can
be ascribed to Ni2+ in Ni(OH)2. The existence of NiO and Ni(OH)2 is
due to that the surface atoms on Ni NPs can be easily oxidized to
form Ni oxide and hydroxide when exposed to air in the presence
of water [45]. It should be noted that there are no peaks related to
NiO or Ni(OH)2 in the XRD pattern of Ni0.22 /CB (Fig. 2) and this is
most likely because of the amorphous nature of resulting NiO and
Ni(OH)2. Moreover, the relatively weak peak of metallic Ni is due to
that the XPS signals come from the surface of the sample. As shown
in Fig. 3c, the C 1s spectrum can be deconvolved into ve peaks with
binding energies at 284.6, 285.4, 286.6, 288.2 and 290.2 eV, corresponding to various carbons under different chemical environment
in the catalyst: sp2 carbon, sp3 carbon, C O, C O species and *
transition loss [42].
3.2. Magnetic properties
Magnetic properties of as-prepared Ni0.22 /CB catalyst were measured by vibrating sample magnetometer at 300 K in the applied
magnetic eld sweeping from 5000 Oe to +5000 Oe. The typical
hysteresis loop of Ni0.22 /CB in its magnetic behavior indicates the
soft magnetic nature of the catalyst (Fig. 4). The saturation magnetization (Ms), remanent magnetization (Mr) and coercivity (Hc)
values of Ni0.22 /CB catalyst are 5.19 emu g1 , 1.74 emu g1 and
101.6 Oe, respectively (see the left insert of Fig. 4). This suggests
that Ni0.22 /CB catalyst is expected to be easily separated from the
dispersion system under an external magnetic eld (see the right
insert of Fig. 4).
3.3. Catalytic activity for hydrogenation of nitrophenols
3.3.1. Catalytic hydrogenation of p-NP
The catalytic activity of the as-obtained catalysts was evaluated
by employing the hydrogenation of p-NP into p-AP in the presence
of NaBH4 . As shown in Fig. 5a, the yellow aqueous p-NP solution
exhibited an absorption maximum at 317 nm. Upon the addition
of NaBH4 , the absorption maximum at 400 nm can be attributed
to the formation of 4-nitrophenolate [14,46]. In contrast, though
an excessive amount of NaBH4 (100 times) was added into the
p-NP solution, hydrogenation of p-NP cannot be carried out in the
absence of catalyst, even for a long time of 10 h. Fig. 5b shows the
UVvis absorption spectra of reaction solution in the presence of
Ni0.22 /CB catalyst at a certain time interval. It can be seen that the
Fig. 3. (a) Global XPS spectrum of as-prepared Ni0.22 /CB catalyst; (bc) Ni 2p and C
1s core-level XPS spectra of Ni0.22 /CB catalyst.
412
Fig. 4. Magnetic hysteresis loop of Ni0.22 /CB catalyst at the temperature of 300 K. The
inserts shows the magnetic hysteresis loop in low eld zone (left) and the dispersion
system after magnetic separation using an external magnet (right).
c
= kt
c0
ln c = kt + lnCo
(1)
(2)
Fig. 5. (a) UVvis absorption spectra of p-NP before and after adding NaBH4 and its reduction product p-AP; (b) UVvis absorption spectra of p-NP catalyzed by Ni0.22 /CB
catalyst at a certain time interval; (c) c/c0 versus time for the hydrogenation of p-NP over different catalysts; (d) Pseudo-rst-order plot of ln(c/c0 ) against reaction time for
the hydrogenation of p-NP over different catalysts.
413
Fig. 6. (a) The relationship between kinetic constant and actual Ni content; (bc) Pseudo-rst-order plot of ln(c/c0 ) against reaction time for the hydrogenation of p-NP
catalyzed by Ni and Ni0.22 /CB catalysts at different temperatures; (d) Plot of lnk against 1/T for the catalytic reduction of p-NP.
Table 1
Pseudo-rst-order kinetics study of p-NP reduction over different catalysts at
30 C a .
Entry
Catalyst
k/ (min1 )
R2
1
2
3
4
5
6
7
Ni0.002 /CB
Ni0.11 /CB
Ni0.22 /CB
Ni0.33 /CB
Ni0.41 /CB
Ni0.49 /CB
Ni
0.0136
0.3628
0.5970
0.3921
0.0653
0.0376
0.0852
0.9921
0.9900
0.9959
0.9910
0.9912
0.9970
0.9898
a
p-Nitrophenol (0.5 mmol L1 , 50 mL), catalyst suspension (0.5 mg mL1 , 2 mL),
NaBH4 (0.1 g), 30 C.
catalyst were chosen as the samples to evaluate the effect of temperature on the reduction of p-NP since the reaction temperature
is one of essential factors for the reduction of p-NP. The catalytic
hydrogenation of p-NP over Ni0.22 /CB and unsupported Ni catalyst
were carried out at four different temperatures ranging from 20 C
to 50 C with an excessive amount of NaBH4 (100 times) under
ambient pressure. As shown in Fig. 6b and c, the rate constant k
increases with the rise of temperature. According to the Arrhenius equation (Eq. (3)) and the linear relationship of lnk against
1/T (Eq. (4), Fig. 6d), the apparent activation energies (Ea ) of the
catalytic hydrogenation of p-NP over Ni0.22 /CB and unsupported
Ni catalyst are calculated to be 80.75 kJ mol1 and 129.31 kJ mol1 ,
respectively, indicating that combination of Ni nanoparticles and
carbon black greatly reduces the activation energy, which facilitates
the reaction at lower temperatures and energy saving.
Ea
k = Ae RT
ln k = (
Ea 1
) + ln A
R T
(3)
(4)
414
Table 2
Substituent effects on the catalytic hydrogenation of nitrophenolsa .
Entry
1
2
3
4
5
6
7
8
9
a
Catalyst
Solvent
Ni0.22 /CB
H2 O
Ni0.22 /CB
MeOH
Ni
H2 O
Product
Conversion(%)
Conversion(%)
o-AP
m-AP
p-AP
o-AP
m-AP
p-AP
o-AP
m-AP
p-AP
5
5
5
3
3
3
5
5
5
54.4
87.6
87.0
85.7
100
100
46.1
54.5
58.6
15
15
15
5
5
5
15
15
15
100
100
100
100
100
100
85.7
100
89.7
p-Nitrophenol (0.5 mmol L1 , 50 mL), catalyst suspension (0.5 mg mL1 , 2 mL), NaBH4 (0.1 g), 30 C.
Fig. 7. Cycling performance of Ni and Ni0.22 /CB catalysts for p-NP reduction.
415
Scheme 2. Hydrogenation process of p-NP with several intermediate products by using Ni0.22 /CB catalyst.
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