Hydrogenation of 1-nitroanthraquinone to 1-aminoanthraquinone catalyzed by bimetallic cuptx nanoparticles

Article abstract of DOI:10.1166/jnn.2019.16577

Bimetallic CuPtx nanoparticles were prepared in ethanol solution by the wet chemical reduction method using Cu(NO₃)₂ and H₂PtCl₆ as starting materials, hydrazine hydrate as a reductant, and polyvinyl pyrrolidone as an organic modifier. The average particle sizes of Cu and Pt nanoparticles were 60 nm and 3 nm, respectively. The small-sized Pt nanoparticles were evenly anchored at the surfaces of large-sized Cu nanoparticles, forming Cu@Pt core-shell structured nanocomposites. In the bimetallic CuPtx nanoparticles, electron was transferred from platinum to copper species, which increased the selectivity of 1-aminoanthraquinone by suppressing the high hydrogenation activity of metallic platinum. The CuPt_0.1 bimetallic nanoparticles exhibited higher catalytic activity for the hydrogenation of 1-nitroanthraquinone to 1-aminoanthraquinone than both monometallic Cu and Pt nanoparticles. Over the CuPt_0.1 catalyst, the selectivity of 1-aminoanthraquinone was 99.3% at the 1-nitroanthraquinone conversion of 98.9%.

Full text of DOI:10.1166/jnn.2019.16577

Article
Journal of
Nanoscience and Nanotechnology
Vol. 19, 5906–5913, 2019
Copyright © 2019 American Scientific Publishers
All rights reserved
Printed in the United States of America
www.aspbs.com/jnn
Hydrogenation of 1-Nitroanthraquinone to
-Aminoanthraquinone Catalyzed by Bimetallic
1
CuPt Nanoparticles
x
∗
Chenchen Yang, Aili Wang, and Hengbo Yin
Faculty of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China
Bimetallic CuPtx nanoparticles were prepared in ethanol solution by the wet chemical reduction
method using Cu(NO ꢀ and H PtCl as starting materials, hydrazine hydrate as a reductant, and
3
2
2
6
polyvinyl pyrrolidone as an organic modifier. The average particle sizes of Cu and Pt nanoparticles
were 60 nm and 3 nm, respectively. The small-sized Pt nanoparticles were evenly anchored at the
surfaces of large-sized Cu nanoparticles, forming Cu@Pt core–shell structured nanocomposites.
In the bimetallic CuPtx nanoparticles, electron was transferred from platinum to copper species,
which increased the selectivity of 1-aminoanthraquinone by suppressing the high hydrogenation
activity of metallic platinum. The CuPt0ꢁ1 bimetallic nanoparticles exhibited higher catalytic activity
for the hydrogenation of 1-nitroanthraquinone to 1-aminoanthraquinone than both monometallic Cu
and Pt nanoparticles. Over the CuPt0ꢁ1 catalyst, the selectivity of 1-aminoanthraquinone was 99.3%
at the 1-nitroanthraqui InPo :n 4e 6c . o1 n4 v 8e .r1s 1i o 5n . 8o 3f 9O8 n. 9: %F .ri, 17 May 2019 15:28:59
Copyright: American Scientific Publishers
Keywords: Bimetallic CuPt Nanoparticles, 1-Nitroanthraquinone, Hydrogenation.
x
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1
. INTRODUCTION
catalytic performances for chemical reactions than
monometallic nanoparticles. Bimetallic AuPd nanoparti-
cles exhibited excellent catalytic activity for the selective
oxidation of methane to methanol with a high selectiv-
1
-Aminoanthraquinone is an important chemical widely
1
–3
4
used for the preparation of dyes, fluorescers, anticancer
medicals, corrosion inhibitors, chemical sensors, and
biochemicals.
5
6ꢀ7
8
ꢀ
12
ity of 92% at 50 C in an aqueous solution. Au Cu
3
Currently, 1-aminoanthraquinone is commercially pro-
duced via the reduction of 1-nitroanthraquinone with
sodium sulfite and/or sodium sulfide at 120 C,
nanoparticles exhibited higher catalytic activity for the
electrochemical reduction of CO than both monometallic
2
ꢀ
13
Au and Cu nanoparticles. Bimetallic PdPt nanoparticles
accompanied by the formation of sodium sulfate
were two and a half times more active in the oxygen
reduction reaction than Pt/C catalyst and five times more
active than commercial Pt black catalyst. The interaction
between two metals in bimetallic nanoparticles plays an
important role in the catalytic reactions.
(
500 tons of sodium sulfate aqueous solution per ton
1
4
of 1-aminoanthraquinone). The organic-containing sodium
sulfate aqueous solution caused a severe pollution prob-
lem. To avoid the pollution, researchers have been seek-
ing alternative catalytic reduction of 1-nitroanthraquinone
In our present work, we found that bimetallic CuPt
nanoparticles could effectively catalyze the hydrogenation
9
with hydrogen over various catalysts, such as Pd/C,
1
0
9ꢀ11
Pd/Al O , and Ni
catalysts in China, giving the
2
3
of 1-nitroanthraquinone with H to 1-aminoanthraquinone.
2
1
-aminoanthraquinone yield of ca. 90%. Pd-based catalysts
The structural effect of the bimetallic CuPt nanoparticles
on the reduction reaction was analyzed and discussed.
exhibited good catalytic activity for the hydrogenation
of 1-nitroanthraquinone to 1-aminoanthraquinone. How
to increase the selectivity of 1-aminoanthraquinone and
decrease catalyst cost is still worthy of investigation.
Recently, bimetallic nanoparticles have attracted
researcher’s attention because they exhibited better
2
2
. EXPERIMENTAL DETAILS
.1. Materials
Hexachloroplatinic acid hexahydrate (H PtCl · 6H O,
2
6
2
>
98%), copper nitrate trihydrate (Cu(NO ꢁ · 3H O,
3
2
2
∗
Author to whom correspondence should be addressed.
>99%), hydrazine hydrate (N H · H O, 85%), polyvinyl
2
4
2
5906
J. Nanosci. Nanotechnol. 2019, Vol. 19, No. 9
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doi:10.1166/jnn.2019.16577

Yang et al.
Hydrogenation of 1-Nitroanthraquinone to 1-Aminoanthraquinone Catalyzed by Bimetallic CuPt Nanoparticles
x
pyrrolidone (PVP, K30), sodium hydroxide (96%),
anhydrous ethanol (>99.7%), 1-nitroanthraquinone
microscope (JSM-6010 PLUS/LA), operating at an accel-
erating voltage of 15 kV.
(
95%), 1-aminoanthraquinone (97%), and N ,N -dimethyl-
The X-ray photoelectron spectra (XPS) of the sam-
ples were performed on a Thermo ESCALAB 250Xi
X-ray photoelectron spectrometer with monochrome
Al Kꢂ ꢅhꢆ = 1486ꢇ6 eV) as X-ray excitation source.
The XPS of the samples were calibrated by using Cls of
formamide (DMF, >99.5%) were of analytical reagent
grade and were purchased from Sinopharm Group Co. Ltd.
2
.2. Preparation of Bimetallic CuPt Nanoparticles
x
2
84.6 eV as the internal standard.
Inductively coupled plasma spectrometer (ICP) analyses
Bimetallic CuPt nanoparticles were prepared by the wet
x
chemical reduction method using hydrazine hydrate as
a reductant and PVP as an organic modifier. A typical
preparation procedure was described as follows. Firstly,
were performed using a VISTA–MPX instrument to ver-
ify the atomic ratio of Cu and Pt in the bimetallic CuPt
samples.
x
−
1
given amount of H PtCl ·6H O (0.0386 mol L ꢁ ethanol
2
6
2
solution and 26 mL of organic modifier (10 wt% of
Cu(NO ꢁ · 3H O) ethanol solution were mixed. Sixty
2.4. Evaluation of Catalytic Performance
3
2
2
−1
milliliters of copper nitrate (0.1667 mol L ꢁ ethanol solu-
Catalytic hydrogenation of 1-nitroanthraquinone with H2
was performed in a 500 mL stainless steel autoclave and
stirred with a magnetic driven stirrer. The autoclave was
charged with 3 g of 1-nitroanthraquinone in 150 mL of
tion was added into the above solution under stirring.
ꢀ
After the mixed solution was heated to 60 C, the pH
value of the solution was adjusted to 10 with a NaOH
−
1
(
1.0 mol L ꢁ ethanol solution. And then, 20 mL of
DMF solution and appointed amount of CuPt nanopar-
x
−1
hydrazine (7.5 mol L ꢁ ethanol solution was added drop-
wise at a rate of 1.2 mL min . The reduction reaction
lasted for 4 h with gentle stirring. The color of the reac-
tion solution became black, indicating that the Cu and
Pt were reduced to metallic Cu and Pt . The CuPt
ticles. The autoclave was purged with N2 for 10 min
to replace air inside. And then, pure H2 was pressur-
ized into the autoclave and the reaction solution was
heated to specified reaction temperatures. When the reac-
tion temperature reached the specified value, the stirring
rate was increased to 400 rpm. After reacting for a period
of time, the reaction was quenched by running cooling
water through a cooling coil in the autoclave. The products
−1
2
+
4
+
0
0
x
nanoparticles were cooled to room temperature, centrifu-
gated at 9000 rpm, and washed with anhydrous ethanol
for 6 times. The resultant bimetallic CuPt nanoparticles
x
were kept in anhydrous ethanol. TI hP e: 4a t6o . m1 4i c8 .r 1a t1i o5 . o8 f3 POt nt o: Fri, 17 May 2019 15:28:59
were analyzed using high performance liquid chromatogra-
phy (HPLC). A reverse-phase column (Innoval ASB C18,
Cu was changed by the volume of H PC t Co pl y·r 6i gH ht O: Ae mt h ea nr i oc la n Scientific Publishers
2
6
2
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solution.
5
mm, 4.6 mm×250 mm) and a UV detector (ꢃ = 254 nm)
For the purpose of comparison, monometallic Cu
nanoparticles and monometallic Pt nanoparticles were also
prepared according to the above-mentioned procedures.
ꢀ
were used for analysis at 30 C. A mixture of water and
methanol of chromatographic grade (v/v, 20/80) was used
−1
as a mobile phase at a flow rate of 1.0 mL min . The con-
centrations of the products and 1-nitroanthraquinone were
analyzed by the external standard method.
2
.3. Characterization
The crystal phases of the as-prepared Cu, Pt, and CuPtx
nanoparticle samples were determined by X-ray powder
diffraction (XRD). The XRD spectra of the samples were
recorded on a diffractometer (D8 super speed Bruke-
3
. RESULTS AND DISCUSSION
3
.1. Chemical Structure and Composition
Analyses by XRD and ICP
The XRD patterns showed that the XRD peaks of the
AEX Company, Germany) using Cu Kꢂ radiation (ꢃ =
ꢀ
1
8
.54056 Å) at room temperature, scanning from 30 to
ꢀ
monometallic copper sample appeared at (2ꢄꢁ 43.3, 50.4,
5 (2ꢄꢁ.
ꢀ
Transmission electron microscopy (TEM) images are
and 74.0 , respectively, which were consistent with the
obtained using a microscope (JEM-2100) operated at an
acceleration voltage of 200 kV to characterize the mor-
phologies and particle sizes of the resultant nanoparticles.
TEM specimens were prepared by dropping ethanol sus-
pension of nanoparticle sample onto a copper grid. The
data used for calculating the particle sizes for each sample
were measured from the TEM images by counting at least
(111), (200), and (220) crystal planes of face-centered
cubic metallic copper (JCPDS 04-0836) (Fig. 1). The XRD
peaks of the monometallic platinum sample appeared at
39.7, 46.3, 67.5, and 81.2 , corresponding to the (111),
(200), (220), and (311) crystal planes of metallic platinum
(JCPDS 04-0802), respectively.
ꢀ
For the bimetallic CuPt samples, the XRD peaks of
x
1
00 individual particles. The average particle size of the
metallic copper were detected. However, no XRD peaks
of metallic platinum were found. It is possibly for the
reason that the amount of platinum was too small to be
detected by XRD technique and/or that platinum particles
with small sizes were well dispersed in the samples. Inter-
estingly, it was found that the XRD peaks of the metallic
metallic nanoparticles was calculated by a weighted aver-
age method based on the size of every individual counted
particle.
The EDX and EDS elemental mapping images of the
bimetallic samples were recorded on a scanning electron
J. Nanosci. Nanotechnol. 19, 5906–5913, 2019
5907

Hydrogenation of 1-Nitroanthraquinone to 1-Aminoanthraquinone Catalyzed by Bimetallic CuPt Nanoparticles
Yang et al.
x
starting materials (Table I). Copper and platinum ions
could be effectively reduced to their metallic states under
our present experimental conditions.
•
•
•
Cu
CuPt0.01
CuPt0.03
CuPt0.04
3
.2. Morphology, Particle Size, and EDS Elemental
Mapping Analyses
The TEM images of the monometallic Cu and Pt sam-
ples show that the monometallic copper sample was com-
posed of Cu nanoparticles with the average particle size of
CuPt0.05
CuPt0.07
6
0 nm and the monometallic platinum sample was com-
CuPt0.1
posed of extreme fine Pt nanoparticles with the average
particle size of 3 nm (Figs. 2(a, b)). For the CuPt sam-
Pt
♦
♦
♦
♦
x
ples, they were composed of both Pt and Cu nanoparticles
3
0
40
50
60
70
80
(
Figs. 2(c–h)). The average particle sizes of the Cu and
2
θ (º)
Pt nanoparticles were similar to those of monometallic Cu
and Pt nanoparticles, respectively. The size distributions of
the Pt nanoparticles in the CuPt samples were in a nar-
Figure 1. The XRD patterns of the bimetallic CuPt , monometallic Cu,
and monometallic Pt nanoparticles. •, metallic Cu; ꢀ, metallic Pt.
x
x
rower range of 1–7 nm (Table I). The TEM images clearly
show that the Pt nanoparticles were well coated on the
surfaces of Cu nanoparticles. The coating extent increased
with the increase in the Pt/Cu atomic ratios.
Additionally, the EDS elemental mapping images show
the uniform distributions of Cu and Pt atoms through-
out the selected samples, implying that the metallic Pt
nanoparticles were well dispersed in the bimetallic CuPtx
samples (Fig. 3). The EDX analysis showed that the
atomic ratios of Pt to Cu increased with the increase in the
copper in the bimetallic CuPt samples shifted to lower
x
2
ꢄ values as compared with those of monometallic Cu
sample. The shift extents of XRD peaks increased with
the increase in platinum content. When the atomic ratio
of Pt to Cu was increased to 0.1:1, the XRD peaks of
(
111), (200), and (220) crystal planes of metallic copper
ꢀ
shifted, respectively, by 0.24, 0.20, and 0.08 as compared
with those of monometallic copper sample. The results
indicated that there was an interaction between metal-
lic copper and metallic platinumI Pi n: 4t h6e .1b 4i m8 . e1 t 1a l5l i. c8 3C Ou Pn t: Fri, 1P 7t c Mo na t ye n 2t s0 1( T9 a b1 l5e : 2I I8) .: 5A9 nd these values of the Pt/Cu ratios
x
Copyright: American Scientific Publishers
nanoparticles.
were larger than those analyzed by ICP analysis. Com-
bined both EDX and EDS elemental mapping analyses, it
is reasonable to conclude that Pt nanoparticles could be
well coated on the surfaces of Cu nanoparticles.
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The crystallite sizes of Cu(111) in the samples were
calculated according to Scherrer’s equation and the data
are listed in Table I. The crystallite sizes of Cu(111) in
both monometallic Cu and bimetallic CuPt samples were
x
around 20 nm, indicating that metallic copper nanopar-
ticles were present in the as-prepared samples. On the
other hand, the ICP analysis showed that the composi-
3.3. Surface Chemical State Analysis by XPS
The surface chemical structures of the monometallic
Cu, monometallic Pt, and representative bimetallic CuPtx
samples were analyzed by XPS technique (Fig. 4).
tions of the CuPt samples were close to those in their
x
Table I. The physicochemical properties of monometallic Cu, monometallic Pt, and bimetallic CuPt nanoparticles and their catalytic activities in the
x
catalytic hydrogenation of 1-nitroanthraquinone to 1-amioanthraquinone.
Selectivities (%)
Atomic
ratios
of Cu/Pt
Crystallite sizes
of metallic
Cu(111) (nm)
Average particle
sizes of
Conversions of
1-nitroanthraquinon
(%)
d
e
1-amino-
1-amino-
Reaction rates
a
b
c
−1 −1
(mol1-NAQ molPt h )
Catalysts
Pt (nm)
anthraquinone
hydroquinone
Cu
–
19.2
17.5
19.7
20.1
19.8
19.5
24.0
1.5 (Pt)
1.5 (Pt)
60.0, (21–116) (Cu)
3.3, (2–5)
3ꢇ3
5ꢇ9
8ꢇ4
17ꢇ4
36ꢇ9
66ꢇ7
98ꢇ9
98ꢇ0
100
100
99.8
99.6
99.7
99.6
99.4
99.3
78.5
61.9
0
–
CuPt0ꢇ01
CuPt0ꢇ03
CuPt0ꢇ04
CuPt0ꢇ05
CuPt0ꢇ07
1:0.01
1:0.03
1:0.04
1:0.05
1:0.07
1:0.11
–
0ꢇ2
0ꢇ4
0ꢇ3
0ꢇ4
0ꢇ6
0ꢇ7
21ꢇ5
38ꢇ1
6ꢇ4
3ꢇ2
5ꢇ1
8ꢇ9
12ꢇ1
12ꢇ7
101
–
3.2, (1–5)
3.0, (1–6)
3.6, (2–6)
3.0, (1–5)
2.9, (1–7)
3.0, (1–6)
3.0, (1–6)
CuPt0
ꢇ1
f
Pt
g
Pt
–
Notes: aThe atomic ratios of Cu/Pt were analyzed by using ICP. bThe crystallite sizes of metallic Cu(111) and Pt(111) were calculated according to the Scherrer’s equation.
c
d
The average particle sizes and size distributions of metallic Cu and Pt were determined according to their TEM images. The reaction conditions: catalyst, 0.18 g; 3 g of
ꢀ
e
1
-nitroanthraquinone was dissolved in 150 N,N-dimethylformamide; 140 C for 4 h; H2 pressure, 0.5 MPa. Reaction rate = reacted 1-nitroanthraquinone (mol)/reaction
f ꢀ g
time/platinum amount (mol) in catalyst.
The catalyst loading of monometallic Pt was the same as that in CuPt0ꢇ1 catalyst. The reaction times were 0.5 and 4 h, respectively.
5908
J. Nanosci. Nanotechnol. 19, 5906–5913, 2019

Yang et al.
Hydrogenation of 1-Nitroanthraquinone to 1-Aminoanthraquinone Catalyzed by Bimetallic CuPt Nanoparticles
x
IP: 46.148.115.83 On: Fri, 17 May 2019 15:28:59
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Figure 2. TEM images of monometallic Cu, monometallic Pt, and bimetallic CuPtx samples and particle size distributions of Cu nanoparticles in
monometallic Cu sample and Pt nanoparticles in bimetallic CuPt samples. (a) Monometallic Cu sample; (b) monometallic Pt sample; and (c–h) bimetal-
x
lic CuPt0ꢇ01, CuPt0ꢇ03, CuPt0ꢇ04 , CuPt0ꢇ05, CuPt0ꢇ07, and CuPt0ꢇ1 samples.
+
0
The binding energies of Cu2p3/2 and Cu2p1/2 of the
these samples were Cu and/or Cu because no satellite
1
5
monometallic Cu, CuPt0ꢇ05, and CuPt0ꢇ1 samples were
peak at 942.5 eV was found. The binding energy of Cu2p
slightly shifted to a lower value with the increase in Pt
content.
9
32.5, 952.3; 932.4, 952.2; 932.3, 952.1 eV, respectively
(
Fig. 4(a)). The chemical states of copper component in
J. Nanosci. Nanotechnol. 19, 5906–5913, 2019
5909

Hydrogenation of 1-Nitroanthraquinone to 1-Aminoanthraquinone Catalyzed by Bimetallic CuPt Nanoparticles
Yang et al.
x
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Figure 3. EDX patterns and EDS elemental mapping images of bimetallic CuPtx samples. (a–f) bimetallic CuPt0ꢇ01, CuPt0ꢇ03, CuPt0ꢇ04, CuPt0ꢇ05
,
CuPt0ꢇ07, and CuPt0ꢇ1 samples.
To ascertain the chemical states of the surface copper
species, the XAES peaks were deconvoluted (Fig. 4(b)).
Using Gaussian-Lorentzian bands with the peak positions
peaks were deconvoluted into two symmetrical peaks.
According to the deconvolution results, the surface copper
species of the monometallic Cu, CuPt , and CuPt sam-
0
ꢇ05
0ꢇ1
+
0 16ꢀ17
+
0
at ca. 915 and 918 eV for Cu and Cu ,
the XAES
ples were composed of Cu and metallic Cu components.
5910
J. Nanosci. Nanotechnol. 19, 5906–5913, 2019

Yang et al.
Hydrogenation of 1-Nitroanthraquinone to 1-Aminoanthraquinone Catalyzed by Bimetallic CuPt Nanoparticles
x
Table II. Cu/Pt atomic ratios on the surfaces of bimetallic CuPtx
a
nanoparticles analyzed by EDX.
Cu2p3/2
Samples
CuPt0ꢇ01 CuPt0ꢇ03 CuPt0ꢇ04 CuPt0ꢇ05 CuPt0ꢇ07 CuPt0ꢇ1
Cu2p1/2
Cu/Pt atomic ratios 1:0.02 1:0.03 1:0.05 1:0.06 1:0.10 1:0.11
Cu
+
0
Their Cu /Cu ratios were 2.7:1, 4.6:1, and 8:1. The ratios
+
0
of surface Cu to Cu were increased with the Pt content.
The high oxidation state at the Cu surface was probably
caused by the oxidation of metallic Cu when the CuPtx
CuPt0.05
0
samples were exposed in air during the sample character-
ization. The presence of Pt probably promoted the oxida-
tion of metallic Cu .
CuPt0.1
0
9
60
955
950
945
940
935
930
925
920
915
The binding energies of Pt4f7/2 and Pt4f5/2 of the
Binding energy (eV)
monometallic Pt, CuPt , and CuPt samples were 71.2,
0
ꢇ1
0ꢇ05
b
Cu+
7
4.6; 71.3, 74.8; 71.8, 75.2 eV, respectively (Fig. 4(c)).
The chemical state of platinum component in these sam-
Cu0
0
18–22
ples was metallic Pt .
The binding energies of Pt4f
CuPt0.1
of the CuPt samples shifted to higher values as compared
x
with the monometallic Pt. The XPS analysis revealed that
there was an interaction between platinum and copper
Cu+
components in the CuPt samples. According to the shift
of Cu2p and Pt4f , it could be suggested that electron was
x
Cu0
CuPt0.05
transferred from platinum to copper species.
3
.4. Catalytic Hydrogenation of 1-Nitroanthraquinone
Cu+
The reaction processes for the catalytic hydrogenation of
IP: 46.148.115.83 On: Fri, 17 May 2019 15:28:59
0
Cu
1
1
-nitroanthraquinone are shown in Scheme 1, in which
Copyright: American Scientific Publishers
-aminoanthraquinone and 1-aminohydroquinoneD aer lei v se t ra e- d by Ingenta
Cu
ble products. 1-Nitrosoanthraquinone and 1-hydroxy-
aminoanthraquinone as the intermediates could be rapidly
and subsequently hydrogenated to 1-aminoanthraquinone.
922
920
918
916
914
912
910
Kinetic energy (eV)
1
1
-Aminoanthraquinone could be further hydrogenated to
-aminohydroquinone.
c
Pt4f7/2
The conversion of 1-nitroanthraquinone was only 3.3%
Pt4f5/2
ꢀ
over the monometallic Cu catalyst at 140 C for 4 h
(
Table I). With increasing the Pt content in the bimetal-
lic CuPtx catalysts, the conversion increased to 98.9%
at a Pt/Cu atomic ratio of 0.1:1. The selectivity of
1
-aminoanthraquinone was above 99% over the monometal-
lic Cu and all CuPtx catalysts. Interestingly, when the
Pt
monometallic Pt nanoparticles were used as the catalysts
with the Pt content equivalent to that in CuPt0ꢇ1 at 140 C
ꢀ
CuPt0.1
for 0.5 h, the selectivity of 1-aminoanthraquinone was
CuPt0.05
7
1
8.5% at the conversion of 1-nitroanthraquinone of 98%.
-Aminohydroquinone with the selectivity of 21.5% was
8
0
78
76
74
72
70
68
66
formed as the by-product via hydrogenation of resultant
Binding energy (eV)
1
4
-aminoanthraquinone. Upon increasing the reaction time to
h, the conversion of 1-nitroanthraquinone reached 100%,
Figure 4. XPS of Cu 2p and Pt 4f of the representative monometal-
lic Cu, monometallic Pt, and bimetallic CuPtx catalysts. (a) Cu 2p;
the selectivity of 1-aminoanthraquinone decreased to
1.9% meanwhile the selectivity of 1-aminohydroquinone
(b) deconvolution of Cu XAES peaks; (c) Pt 4f .
6
increased to 38.1%. Over the monometallic Pt nanoparti-
cles, the desired 1-aminoanthraquinone could be further
hydrogenated to produce 1-aminohydroquinone as com-
When the bimetallic CuPtx catalysts with the Pt/Cu
atomic ratios of 0.05:1–0.1:1 were used as the catalysts,
their reaction rates ranged from 8.9 to 12.7 mol
1
-NAQ
−
1
−1
pared with the bimetallic CuPt nanoparticles.
mol
h , which were much less than that of the
x
Pt
J. Nanosci. Nanotechnol. 19, 5906–5913, 2019
5911

Hydrogenation of 1-Nitroanthraquinone to 1-Aminoanthraquinone Catalyzed by Bimetallic CuPt Nanoparticles
Yang et al.
x
O
O
NO2
O
O
NHOH
monometallic Pt catalyst. The results revealed that
the interaction between Pt and Cu in bimetallic
N
H2
Catalyst
H2
Catalyst
CuPt nanoparticles favored the catalytic hydrogenation
x
O
O
O
1
-nitroanthraquinone to 1-aminoanthraquinone, suppress-
1
-Nitroanthraquinone 1-Nitrosoanthraquinone 1-Hydroxyaminoanthraquinone
ing the nonselective and high hydrogenation activity of the
monometallic Pt nanoparticles.
H2 Catalyst
O
O
NH2
OH NH2
OH
3
.5. Effect of Reaction Temperature, Reaction
Time, and Catalyst Loading
H2
Catalyst
The bimetallic CuPt0ꢇ1 nanoparticles were used as the
model catalysts to investigate the effect of reaction param-
eters, such as reaction temperature, reaction time, and cat-
alyst loading, on the hydrogenation reaction (Fig. 5). Upon
1
-Aminohydroquinone
1-Aminoanthraquinone
Scheme 1. Catalytic hydrogenation processes of 1-nitroanthraquinone.
ꢀ
a
100
100
80
60
40
20
0
increasing the reaction temperature to 130 C, the con-
version of 1-nitroanthraquinone increased to 98%. The
selectivity of 1-aminoanthraquinone was above 99% at
different reaction temperatures (Fig. 5(a)). With prolong-
8
6
4
2
0
0
0
0
0
ꢀ
ing the reaction time to 4 h at 140 C, the conver-
sion of 1-nitroanthraquinone reached 98.9% (Fig. 5(b)).
Increasing catalyst loading favored the conversion of
1-nitroanthraquinone to 1-aminoanthraquinone (Fig. 5(c)).
The results showed that bimetallic CuPt0ꢇ1 nanoparticles
exhibited excellent selectivity for the hydrogenation of
1-nitroanthraquinone to 1-aminoanthraquinone.
100
110
120
130
140
Temperature (ºC)
b
100
100
4
. CONCLUSIONS
8
6
4
2
0
0
0
0
0
IP: 46.148.11
80
5
.83 On: Fri, 17 May 2019 15:28:59
Bimetallic CuPt nanoparticles were prepared by the wet
x
Copyright: American Scientific Publishers
chemical reduction method. The small-sized Pt nanopar-
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ticles were well dispersed on the surfaces of large-sized
40
20
0
Cu nanoparticles. There was an interaction between Pt
nanoparticle and Cu nanoparticle in the bimetallic CuPtx
nanoparticles. The bimetallic CuPt0ꢇ1 nanoparticles exhib-
ited high catalytic activity for the selective hydrogenation
of 1-nitroanthraquinone to 1-aminoanthraquinone under
mild reaction temperature. The bimetallic CuPt0ꢇ1 nanopar-
ticles may have potential application for the hydrogenation
reaction.
0
1
2
3
4
5
6
7
8
9
Time (h)
c
1
00
100
80
60
40
20
0
8
6
4
2
0
0
0
0
Acknowledgments: This work was financially sup-
ported by National Natural Science Foundation of China
(
21506078) and China Postdoctoral Science Foundation
(2016M601739). We also sincerely thank Prof. Kangmin
Chen for his helpful support on TEM analysis.
0
0
References and Notes
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Received: 4 August 2018. Accepted: 10 September 2018.
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