Selective hydrogenation of p-chloronitrobenzene over an Fe promoted Pt/AC catalyst

Article abstract of DOI:10.1039/c7ra04700b

Activated carbon supported Pt (Pt/AC) and Fe modified Pt (Pt-Fe/AC) catalysts have been investigated for selective hydrogenation of p-chloronitrobenzene to p-chloroaniline. It was found that the incorporation of an appropriate amount of Fe (4 wt%) resulte

Full text of DOI:10.1039/c7ra04700b

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Selective hydrogenation of p-chloronitrobenzene
over an Fe promoted Pt/AC catalyst
Cite this: RSC Adv., 2017, 7, 29143
Hu Chen, Daiping He, * Qingqing He, Ping Jiang,
and Wensheng Fu
Gongbing Zhou
Activated carbon supported Pt (Pt/AC) and Fe modified Pt (Pt–Fe/AC) catalysts have been investigated for
selective hydrogenation of p-chloronitrobenzene to p-chloroaniline. It was found that the incorporation of
an appropriate amount of Fe (4 wt%) resulted in a remarkable increase in activity and selectivity to p-
chloroaniline, and the catalytic hydrodechlorination over the catalyst was fully suppressed at complete
conversion of p-chloronitrobenzene. X-ray photoelectron spectroscopy (XPS) revealed the electron
Received 26th April 2017
Accepted 28th May 2017
2 3
transfer from Pt nanoparticles to Fe O , leading to the electron-deficient state of the Pt nanoparticles in
DOI: 10.1039/c7ra04700b
the present catalyst, which is responsible for improved performance of the Pt–Fe/AC catalyst for p-
chloronitrobenzene hydrogenation to p-chloroaniline.
rsc.li/rsc-advances
14
deactivation. In most cases, high selectivity is always achieved
at the expense of activity by introducing either transition-metal
1
Introduction
15–17
The reduction of chloronitrobenzenes to chloroanilines is salts or additives that partly poison the active sites.
The
signicant in organic synthesis because the chloroanilines are choice of components is critical in developing an efficient and
the key intermediates of pharmaceuticals, polymers, pesticides, viable catalyst, and due attention should be paid to the inter-
1
explosives, bers, dyes and cosmetics. The traditional methods action between active metal and promoter, since the nature of
that use either the Fe/HCl system (Bechamp reaction) or metal this interaction plays an important role in shaping the activity,
18
suldes inevitably generate large amounts of waste, which selectivity and stability of the catalyst. Mahata N et al. studied
2
requires costly and laborious separation and disposal.
the inuence of Cu on the catalytic properties of Pt/C for the
Synthesis of chloroanilines using catalytic hydrogenation hydrogenation of chloronitrobenzenes. It is found that the
starting with chloronitrobenzenes offers several advantages strong interactions between Pt and Cu result in partial coverage
over chemical reduction, including cheap hydrogen, easy of the Pt surface by Cu. The supercial Cu species activate the
product separation and a nonpolluting process. A severe N]O bond of chloronitrobenzene and also inhibit the
problem related to the catalytic hydrogenation has been the co- adsorption of the desired product chloroaniline. Thus, the
occurrence of the catalytic hydrodechlorination reaction of the bimetallic catalysts exhibited excellent performance in
3
–5
substrates, which signicantly limits the selectivity to chlor- producing selectively chloroanilines (>99%) in comparison to
oanilines and leads to a lot of wastes. Furthermore, hydrogen the Pt/AC catalyst. Moreover, the high catalytic activity of the Pt
chloride produced from the hydrodechlorination is also corro- nanoclusters was maintained.
sive to the reactor. It is highly desirable to develop heteroge-
In this paper, we report the promotional effect of Fe on the
neous catalysts that would ensure the selective reduction of the catalytic performance of Pt/C catalyst. The possible function of
nitro groups while leave intact of the carbon–chlorine bond in Fe in Pt–Fe/AC catalysts is discussed on the basis of catalyst
the same molecule. Many efforts have been devoted to per- characterization and catalytic results.
forming selective hydrogenation of chloronitrobenzenes to
corresponding chloroanilines over a plentiful of metal cata-
6
–11
lysts,
offers the highest selectivity of chloroanilines for this hydro-
including Pt, Pd, Au, Ru, Ni and Ag. The gold catalyst 2 Experimental
2.1 Catalyst preparation
12,13
genation,
but platinum seems to be the best catalyst for
An activated carbon (AC) sample was obtained from Chongqing
Chuandong Chemical Company and was crushed into 220–250
mesh powder. It was washed with distilled water, then dried at
minimizing dechlorination combined with a fast rate of
reduction of the nitro group and being highly resistant to
383 K overnight and calcined in owing air at 523 K for 3 h. The
Pt–Fe/AC catalyst was prepared by a wet impregnation tech-
Key Lab of Green Synthesis and Applications, College of Chemistry, Chongqing Normal
University, Chongqing 401331, China. E-mail: hedaiping@126.com; Fax: +86-23-
nique. Typically, 2.0 g of activated carbon with BET surface area
2
ꢀ1
6
536-2777; Tel: +86-23-6591-0309
3 3
of 411 m g was added to 50 mL aqueous Fe(NO ) (0.03 mol
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ꢀ
1
L
) and the suspension was stirred for 24 h. Then, 1.58 mL
ꢀ
3
ꢀ1
aqueous H PtCl (3.8 ꢁ 10 mol L ) was added dropwise to
2
6
the mixture for 24 h upon continuous stirring. The deposition of
Pt and Fe nanoparticles from the aqueous solution occurred
ꢀ
1
4
when a stoichiometric excess of aqueous NaBH (0.5 mol L )
was added dropwise to the mixture. Stirring was continued for
a further 5 h. The solids were ltered and washed thoroughly
with distilled water until free of chloride ions. The obtained
sample was dried at 383 K for 10 h and calcined in owing air at
different temperature for 5 h. The platinum, iron in the catalyst
was 0.29 wt% and 3.86 wt% according to ICP-AES analysis,
respectively.
2.2 Catalyst characterization
The platinum and iron contents in the 0.3% Pt–4% Fe/AC
catalyst were analyzed by means of inductively coupled Fig. 1 XRD patterns of AC (a) and 0.3% Pt–4% Fe/AC (b).
plasma-atomic emission spectroscopy (ICP-AES) aer the
sample was dissolved in aqua regia. X-ray powder diffraction
22
(XRD) patterns were recorded on a Rigaku D/Max Ultima IV X- assigned to Fe (110) plane were detected in the 0.3% Pt–4% Fe/
ray diffractometer using Cu Ka radiation with accelerating AC catalyst, probably because of the low percentage of metals on
voltage of 40 kV and current of 30 mA. Transmission electron the catalyst and/or the small particle size.
microscopy (TEM) measurement was performed on a JEOL JEM-
Fig. 2 shows the representative TEM images of the 0.3% Pt–
2000EX microscope operated at an accelerating voltage of 120 4% Fe/AC catalyst. As can be seen from the TEM image (Fig. 2a),
kV. An energy-dispersive X-ray (EDX) spectroscopic detecting small black spots can be discerned from the background over
unit was used to collect the EDX spectra for elemental analysis. the 0.3% Pt–4% Fe/AC catalyst. A combined EDX analysis
X-ray photoelectron spectra (XPS) were obtained on an ESCALAB showed that the signal of Pt and Fe could be detected in the
250 X-ray photoelectron spectroscopy using Mg-Ka X-ray as the small black spots (Fig. 2b). Therefore, we conclude that the
excitation source. XPS spectra were calibrated based on the small black spots in Fig. 2a are the images of the Pt and Fe
graphite C 1s peak at 284.6 eV.
.3 Catalyst testing
species. The Fe and Pt particles in the 0.3% Pt–4% Fe/AC
2
The catalytic hydrogenation was carried out with magnetic
stirring (900 rpm) in a 60 mL Teon-lined stainless steel auto-
clave containing 1.0 g of p-chloronitrobenzene (p-CNB) in 8.0
mL ethanol (solvent). The catalyst used in each run of the
reaction was 20.0 mg. The reactor was ushed one time with
2 2
0.5 MPa N and then four times with 0.5 MPa H before it was
pressurized to the desired H pressure and placed in a heat
2
installation maintained at the reaction temperature. The reac-
tion was stopped at a selected time by cooling the reactor in
a ice water bath. The products were analyzed by GC (GC9890)
with an SE-30 capillary column and an FID as detector, using o-
xylene as an internal standard.
3
Results and discussion
3.1 Catalyst characterization
The XRD patterns of the AC support and 0.3% Pt–4% Fe/AC
catalyst are shown in Fig. 1. The AC support shows the char-
acteristic diffraction peaks of graphitized activated carbon at 2q
ꢂ ꢂ ꢂ ꢂ ꢂ
19
¼
24.3 , 35.4 and 43.2 . The minor peaks at 20.7 , 26.5 ,
ꢂ ꢂ ꢂ
9.4 , 50.1 and 68.1 are attributed to the presence of trace
quantity of silica. The XRD pattern of the 0.3% Pt–4% Fe/AC
3
20
catalyst is similar to that of the AC support as we can see
ꢂ
ꢂ
ꢂ
from Fig. 1b. No characteristic diffraction peaks at 39.9 , 46.4 ,
6
Fig. 2 TEM image of 0.3% Pt–4% Fe/AC (a), EDX spectra of the selected
area (b) and size distributions of Pt–Fe particles in the catalyst (c).
ꢂ
21
7.5 index to (111), (200), (220) planes of metallic Pt and 44.4
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Fig. 3 XPS spectrum of Fe 2p3/2 for 0.3% Pt–4% Fe/AC.
Fig. 4 XPS spectra of Pt 4f5/2 for 0.3% Pt/AC (a) and 0.3% Pt–4% Fe/
AC (b).
catalyst have an average diameter of 4.5 nm, with a size distri-
bution from 3 to 7 nm (Fig. 2c), which is consistent with the
absence of characteristic diffraction peaks of Fe and Pt in the
XRD pattern of the 0.3% Pt–4% Fe/AC, suggesting that the Fe
and Pt species on AC support are in a homogenous dispersion
without any obvious aggregation.
reaction observed over the Pt/AC was not detected over the 0.3%
Pt–4% Fe/AC catalyst. Special attention was paid to distinguish
byproducts of the p-CNB hydrogenation reactions with GC-MS.
Any byproduct that amounted to 0.1% in the reaction mixture
can be unambiguously detected in our method of product
analysis. We did not detect any by-products derived from the
hydrodechlorination over the 0.3% Pt–4% Fe/AC catalyst, even
when the reaction time was extended by 30 minutes aer p-CNB
was exhausted, which indicates that the undesired hydro-
dechlorination reaction usually observed over other metal
XPS analyses of the 0.3% Pt/AC and 0.3% Pt–4% Fe/AC
catalysts were performed. The Fe 2p spectrum of the 0.3% Pt–
4
% Fe/AC can be deconvoluted three peaks (Fig. 3). The peaks
3
+
8/3+
2+
can be assigned to Fe in Fe
2
O
3
, Fe
respectively. It is evident that the calcination of the 0.3% Pt–
% Fe/AC at 473 K in air leads to the formation of Fe on AC.
Fig. 4 presents the Pt 4f spectra of the 0.3% Pt/AC and 0.3% Pt–
% Fe/AC catalysts. The Pt 4f7/2 photoelectron peak of the 0.3%
3 4
in Fe O and Fe in FeO,
23
4
2 3
O
27–29
catalysts
data indicate that the electron transfer occurred from Pt to
Fe make the Pt nanoparticles in the 0.3% Pt–4% Fe/AC
can be successfully avoided over the catalyst. XPS
4
Pt/AC catalyst is observed at 71.2 eV (Fig. 4a), which is consis-
tent with the characteristic peak of Pt 4f7/2 for metallic Pt at
2 3
O
2
4
catalyst an electron-decient state. The electron-decient state
of the Pt particles could weaken the extent of electron feedback
from the Pt particles to the aromatic ring in chloroanilines and
7
0
1.1 eV. However, the binding energy of the Pt 4f7/2 level in the
.3% Pt–4% Fe/AC catalyst (Fig. 4b) is 0.9 eV higher than that of
metallic Pt. This reveals the electron transfer and the electron-
25
suppressed the hydrodechlorination reaction. Therefore, the
high selectivity of p-CAN over the 0.3% Pt–4% Fe/AC catalyst
may attribute to the electron-decient state of the Pt
nanoparticles.
decient state of the Pt nanoparticles in the 0.3% Pt–4% Fe/
25
AC catalyst. Wang et al. also observed the same phenom-
enon in the Pt/g-Fe O catalyst. Based on these results, we
2
3
believe that the electron transfer may occur from the Pt particles
to the Fe in the 0.3% Pt–4% Fe/AC catalyst.
2 3
O
3
.2 Catalytic performance
Table 1 Catalytic results of selective hydrogenation of p-CNB over
different catalysts
a
Table 1 shows the catalytic properties of the 4% Fe/AC, 0.3% Pt/
AC and 0.3% Pt–Fe/AC catalysts for hydrogenation of p-CNB at
Sel. (%)
2
303 K, 1.0 MPa H . No reaction of p-CNB was observed in the
p-CNB conv./%
b
c
absence of the catalyst and over the 4% Fe/AC catalyst. The Catalyst
(min)
p-CAN
AN
Others
conversion of p-CNB over the 0.3% Pt/AC catalyst was 37% for 40
4
0
0
0
% Fe/AC
.3% Pt/AC
.3% Pt–2% Fe/AC
.3% Pt–4% Fe/AC
n.d. (40)
37 (40)
50 (40)
n.d.
84.0
92.6
94.2
100
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
16.0
7.4
minutes. When the same 0.3% Pt/AC was loaded with 4% Fe,
however, a dramatically high p-CNB conversion (65%) was
achieved under the same reaction conditions, and the selectivity
65 (40)
5.8
to the desired product p-CAN also increased from 84.0% to 0.3% Pt–4% Fe/AC
100 (90)
100 (120)
33 (40)
n.d.
n.d.
7.3
0
0
.3% Pt–4% Fe/AC
.3% Pt–6% Fe/AC
100
92.7
94.2%, which may be attributed to Fe
x y
O species activated the
N]O bond which becomes highly susceptible to hydrogen
26
a
b
c
attack. When Fe loading amount further increases from 4 wt%
to 6 wt%, the conversion of p-CNB decreases from 65% to 33%,
which may be caused by partial coverage of the Pt surface by
n.d.: not detected. AN refers to aniline. Other products were p-
0
0
4,4 -
chloronitrosobenzene,
dichloroazobenzene. Reaction conditions: 20.0 mg catalyst, 1.0 g p-
CNB in 8.0 mL ethanol (solvent), 303 K, 1.0 MPa H
4,4 -dichloroazoxybenzene
and
2
.
x y
excess Fe O . Interestingly, the undesired hydrodechlorination
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Table 2 Effect of calcination temperature on catalytic performance of Table
5
Reusability of 0.3% Pt–4% Fe/AC catalyst for selective
0
.3% Pt–4% Fe/AC for p-CNB hydrogenation
hydrogenation of p-CNB
Sel./%
Sel. (%)
a
a
a
a
Calci. temp./K
p-CNB conv./%
p-CAN
AN
Others
Cycle number
p-CNB conv. (%)
p-CAN
AN
Others
3
4
5
6
83
73
73
23
33
65
57
51
91.4
94.2
93.8
93.2
n.d.
n.d.
n.d.
n.d.
8.6
5.8
6.2
6.8
1
2
3
4
65
52
42
42
94.2
92.7
92.5
92.3
n.d.
n.d.
n.d.
n.d.
5.8
7.3
7.5
7.7
a
a
See the note in Table 1. Reaction conditions are the same as in Table 1.
See the note in Table 1. Reaction conditions are the same as in Table 1.
Table 3 Effect of reaction temperature on catalytic performance of respectively. The conversion increased signicantly to 100%
0
.3% Pt–4% Fe/AC for p-CNB hydrogenation
and the selectivity reached 100% without formation of any
decholorination product when the reaction temperature
increased from 303 K to 333 K. The byproducts produced in the
reaction can be further hydrogenated to the desired product p-
CAN. These data demonstrate that the undesired further
hydrogenation of p-CAN can be avoided over the 0.3% Pt–4% Fe/
AC catalyst in a broad window (303–333 K).
Sel./%
a
a
React. temp./K
p-CNB conv./%
p-CAN
AN
Others
3
3
3
3
03
13
23
33
65
92
100
100
94.2
96.3
98.9
100
n.d.
n.d.
n.d.
n.d.
5.8
3.7
1.1
n.d.
a
See the note in Table 1. Other reaction conditions are the same as in
Table 1.
3.3 Effect of calcination temperature
The hydrogenation properties of the 0.3% Pt–4% Fe/AC calcined
at different temperature are also investigated, and the results are
listed in Table 2. From Table 2, we can see that different calci-
nation temperature of the 0.3% Pt–4% Fe/AC has signicant
inuence on the hydrogenation of p-CNB. The 0.3% Pt–4% Fe/AC
calcined at 473 K shows the best catalytic activity and selectivity
towards p-CAN, which could can be the result of the favorable
2 3
formation of Fe O on AC at 473 K, and the sintering of the Pt
nanoparticles at higher calcination temperature (>473 K).
3.4 Effect of reaction conditions
The reaction temperature also plays a signicant role in the p-
CNB hydrogenation reaction (Table 3). The conversion of p-CNB
and selectivity to p-CAN was 65% and 94.2% at 303 K,
2
Table 4 Effect of H pressure on catalytic performance of 0.3% Pt–4%
Fe/AC for p-CNB hydrogenation
Sel./%
a
a
H
2
pressure/MPa
p-CNB conv./%
p-CAN
AN
Others
0
1
2
3
.5
.0
.0
.0
30
65
100
100
92.9
94.2
98.5
100
n.d.
n.d.
n.d.
n.d.
7.1
5.8
1.5
n.d.
a
See the note in Table 1. Other reaction conditions are the same as in
Table 1.
Fig. 5 TEM image of the 0.3% Pt–4% Fe/AC after catalysis (a) and size
distributions of Pt–Fe particles in the catalyst (b).
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This advantage of the catalyst is clearly shown by the catalytic
RSC Advances
References
properties under the elevated H2 pressure (Table 4). The
conversion of p-CNB and selectivity to p-CAN was 30% and 92.9%
1 R. S. Downing, P. J. Kunkeler and H. van Bekkum, Catal.
Today, 1997, 37, 121.
at 0.5 MPa H , respectively. The conversion increased to 100%
2
and the selectivity reached 98.5% at 2.0 MPa H
2
. It is interesting
2 H. U. Blaser, U. Siegrist, H. Steiner and M. Studer, in Fine
Chemicals through Heterogeneous Catalysis, Wiley-VCH,
Weinheim, 2001, pp. 389–406.
3 M. H. Liu, X. X. Mo, Y. Y. Liu, H. L. Xiao, Y. Zhang, J. Y. Jing,
V. Colvin and W. W. Yu, Appl. Catal., A, 2012, 439–440, 192.
4 S. Ichikawa, T. Seki and T. Ikariya, Adv. Synth. Catal., 2014,
356, 2643.
to note that any by-products derived from the hydro-
dechlorination were not detected, even when all of the p-CNB was
exhausted under 3.0 MPa, which demonstrates a remarkable
feature of the 0.3% Pt–4% Fe/AC catalyst for avoiding successfully
any occurrence of the further hydrogenation of p-CAN even when
very high H pressure is used for the reaction.
2
5
A. B. Dongil, L. Pastor-P ´e rez, J. L. G. Fierro, N. Escalona and
A. Sep u´ lveda-Escriban, Catal. Commun., 2016, 75, 55.
F. C ´a rdenas-Lizana, S. G ´o mez-Quero and M. A. Keane, Appl.
Catal., A, 2008, 334, 199.
7 L. N. Liu, L. N. Xing, C. X. Cheng, L. X. Xia and H. Y. Liu, RSC
Adv., 2016, 6, 31871.
8 Y. C. Liu, C. Y. Huang and Y. W. Chen, Ind. Eng. Chem. Res.,
2006, 45, 62.
9 Y. Y. Fan, H. L. Xiao, N. Sui, M. H. Liu and W. W. Yu, RSC
3
.5 Catalyst stability
6
The recycling procedure of the 0.3% Pt–4% Fe/AC catalyst was
performed for examining the stability of the catalyst. The cata-
lyst aer reaction was separated by centrifugation, washed with
ethanol, dried under vacuum and then reused for the same
reaction. As shown in Table 5, both conversion and selectivity
did not exhibit a considerable decrease for at least 4 cycles. We
checked the Pt, Fe content in the recovered catalyst aer 4 cycles
Adv., 2014, 4, 11788.
and found that there was only a slight loss of Pt (0.02 wt%) and 10 E. Bertolucci, R. Bacsa, A. Benyounes, A. M. Raspolli-Gallett,
Fe (0.35 wt%) in the recovered catalyst. TEM analysis showed
M. R. Axet and P. Serp, ChemCatChem, 2015, 7, 2971.
good dispersion of Pt–Fe particles in the recovered 0.3% Pt–4% 11 F. Cardenas-Lizana, D. Lamey, N. Perret, S. Gomez-Quero,
Fe/AC (Fig. 5a). The average Pt–Fe particle size was 4.6 nm, with
L. Kiwi-Minsker and M. A. Keane, Catal. Commun., 2015,
a size distribution from 3 to 7 nm (Fig. 5b), which is similar to
21, 46.
that in the as-prepared fresh 0.3% Pt–4% Fe/AC catalyst (4.5 12 C. H. Camposa, M. Jofr ´e a, C. C. Torresa, B. Pawelecb,
nm) (Fig. 2c). The as-prepared 0.3% Pt–4% Fe/AC catalyst
showed high stability.
J. L. G. Fierrob and P. Reyesa, Appl. Catal., A, 2014, 482, 127.
13 D. P. He, X. D. Jiao, P. Jiang, J. Wang and B. Q. Xu, Green
Chem., 2012, 14, 111.
1
4 M. H. Liu, W. Y. Yu and H. F. Liu, J. Mol. Catal. A: Chem.,
999, 138, 295.
5 M. Makosch, W. I. Lin, V. Bumb ´a lek, J. S ´a , J. W. Medlin,
K. Hungerb u¨ hler and J. A. van Bokhoven, ACS Catal., 2012,
2
4
Conclusion
1
1
In this study, we have prepared Fe modied Pt nanoparticles
over activated carbon and investigated their catalytic perfor-
mance on the chemoselective hydrogenation of p-chloroni-
trobenzene. It was found that the incorporation of an
appropriate amount of Fe (4 wt%) resulted in a remarkable
increase in activity, and the selectivity to p-chloronitrobenzene
could be up to 100% at complete conversion of p-chloroni-
trobenzene over 0.3% Pt–4% Fe/AC catalyst even at high
temperature and H pressure. X-ray photoelectron spectroscopy
revealed the formation of Fe O and the electron transfer from
Pt nanoparticles to Fe O , leading to the electron-decient state
of the Pt nanoparticles in the present catalyst, which are
responsible for the improved performance of 0.3% Pt–4% Fe/AC
catalyst for p-chloronitrobenzene hydrogenation to p-chlor-
, 2079.
6 S. Furukawa, Y. Yoshida and T. Komatsu, ACS Catal., 2014, 4,
441.
7 K. M o€ bus, D. Wolf, H. Benischke, U. Dittmeier, K. Simon,
U. Packruhn, R. Jantke, S. Weidlich, C. Weber and
B. S. Chen, Top. Catal., 2010, 53, 1126.
1
1
1
1
8 N. Mahata, O. S. G. P. Soaresa, I. Rodr ´ı guez-Ramos,
2
´
˜
M. F. R. Pereira, J. J. M. Orfao and J. L. Figueiredo, Appl.
Catal., A, 2013, 464–465, 28.
2
3
2
3
1
2
2
2
2
9 H. Zhu, W. F. Han, H. F. Chai and H. Z. Liu, Chin. J. Catal.,
2007, 28, 196.
0 P. R. Shukla, S. B. Wang, H. Q. Sun, H. M. Ang and M. Tad ´e ,
Appl. Catal., B, 2010, 100, 529.
1 A. Shukla, R. K. Singha, T. Sasaki and R. Bal, Green Chem.,
oaniline. High reaction temperature and H
favorable for p-CNB hydrogenation to p-CAN over the 0.3% Pt–
% Fe/AC catalyst.
2
pressure are
2015, 17, 785.
4
2 W. J. Li, L. M. Ye, P. Long, J. Chen, H. Ariga, K. Asakurab and
Y. Z. Yuan, RSC Adv., 2014, 4, 29072.
3 J. Gong, K. Yao, J. Liu, Z. W. Jiang, X. C. Chen, X. Wen,
E. Mijowska, N. N. Tian and T. Tang, J. Mater. Chem. A,
2013, 1, 5247.
Acknowledgements
This work was supported by the Science and Technology Inno-
vation Project of Chongqing (cstc2016shmszx20004) and Project 24 L. Olsson and E. Fridell, J. Catal., 2002, 210, 340.
of International Science and Technology Cooperation in
Chongqing (cstc2014gjhz20002).
This journal is © The Royal Society of Chemistry 2017
RSC Adv., 2017, 7, 29143–29148 | 29147

View Article Online
RSC Advances
Paper
2
2
2
5 J. L. Zhang, Y. Wang, H. Ji, Y. G. Wei, N. Z. Wu, B. J. Zuo and 28 H. M. Liu, H. B. Yu, C. R. Xiong and S. H. Zhou, RSC Adv.,
Q. L. Wang, J. Catal., 2005, 229, 114. 2015, 5, 20238.
6 X. X. Han, R. X. Zhou, G. H. Lai and X. M. Zheng, Catal. 29 C. S. Lu, M. J. Wang, Z. L. Feng, Y. N. Qi, F. Feng, L. Ma,
Today, 2004, 93–95, 433.
Q. F. Zhang and X. N. Li, Catal. Sci. Technol., 2017, 7, 1581.
7 C. Lian, H. Q. Liu, C. Xiao, W. Yang, K. Zhang, Y. Liu and
Y. Wang, Chem. Commun., 2012, 48, 3124.
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