Received: December 10, 2014 | Accepted: January 6, 2015 | Web Released: January 14, 2015 CL-141139

Ni0.85Se Nanostructures with Plate-like and Particle Morphologies

and Their Catalytic Performances
Xian-Wen Wang, Kong-Lin Wu,* Meng-Li Zhao, Zai-Xian Zhang, Min Ling,
Kun Liu, Xian-Wen Wei,* Xiaowang Liu, and Ruirui Yun
College of Chemistry and Materials Science, the Key Laboratory of Functional Molecular Solids, Ministry of Education,
Anhui Laboratory of Molecular-Based Materials, Anhui Normal University, Wuhu 241000, P. R. China

(E-mail: konglin@mail.ahnu.edu.cn, xwwei@mail.ahnu.edu.cn)

Ni0.85Se plate-like nanostructures (PNSs) had been prepared
by a template method, and by a similar process, the Ni0.85Se
nanoparticles were obtained by using NiCl2¢6H2O as the nickel
source. The Ni0.85Se nanostructures (NSs) with different shapes
exhibited high catalytic activities for hydrogenation of 4-
nitrophenol (4-NP) with excess NaBH4. To the best of our
knowledge, this may be the first report on using Ni0.85Se NSs as
catalysts for the reduction of 4-NP.
The development of NixSey materials, such as NiSe2 and
Ni3Se2, has attracted considerable attention over the past few
years because of their attractive applications in the fields of con-
ductivity, energy-conversion or -storage device, and sensor.1­4
Specifically, Ni0.85Se micro-/nanocrystals have been explored
extensively because of their unique physical and chemical
properties. For example, Luan and co-workers reported that
hexagonal Ni0.85Se nanoparticles (NPs) were quickly synthe-
sized via a convenient solvothermal reduction process in a flask
at 180 °C for 1 h.4 Qian and co-workers reported a solvothermal
method to synthesize nanocrystalline Ni0.85Se NPs using
NiCl2¢6H2O5 or NiC2O4¢2H2O6 as the Ni source, and elemental
selenium as the Se source, respectively. Zhu and co-workers
prepared spherical, nanocrystalline Ni0.85Se by using NiCl2¢
6H2O as the Ni source and Na2SeO3 as the Se source in a low-
temperature hydrothermal process.7 Wang presented a facile
one-step low-temperature hydrothermal approach for the in situ
growth of Ni0.85Se on conductive glass substrates, which could
be used directly as transparent counter electrodes for dye-
sensitized solar cells without any post-treatment.8 Very recently,
deionized water under ultrasonication for 10 min, followed by
the addition of 2 mL of freshly prepared NaHSe solution (2 M).
Thereafter, the mixture was transferred into a Teflon-lined
stainless-steel autoclave of 60 mL capacity, and was kept at
160 °C for 8 h to obtain the Ni0.85Se PNSs. More importantly,
the as-obtained Ni0.85Se crystals were used as catalysts for the
hydrogenation of 4-nitrophenol (4-NP) into 4-aminophenol
(4-AP) in the presence of NaBH4 in aqueous solution for the
first time. Detailed experimental sections are given in the
Supplementary Information (SI).
In order to obtain the Ni0.85Se PNSs, we first fabricated
the Ni-precursors template using a facile hydrothermal method
(SI). The field-emission scanning electron microscopy (FESEM,
Figure S1a) image of the Ni-precursors shows that they were
composed of plate-like structures. The phase composition of
Ni-precursors was investigated by X-ray diffraction (XRD). All
the strong diffraction peaks in Figure S1b could be indexed
as hexagonal phase Ni2(OH)3Cl (JCPDS No. 02-1085), besides
some weak diffraction peaks for hexagonal phase Ni(OH)2
(JCPDS, No. 14-0117).
Using fresh NaHSe as the selenylation source, the solid
Ni-precursors could be chemically transformed into Ni selenide.
The complete phase conversion was corroborated by XRD
analysis (Figure 1a). Similar results have been obtained in the
case of the XRD patterns of spherical nanoparticles synthesized
by Mostafa.9 The diffraction peaks at about 33.2, 45.0, 50.5,
60.3, 61.8, 69.8, and 71.5° were attributed to the respective
(101), (102), (110), (103), (201), (202), and (004) planes of the
a b
Intensity (arb unit)

Intensity (arb unit)

101

Se
Mostafa and co-workers prepared nanocrystalline Ni0.85Se solid
solution by a simple hydrothermal route.9 Furthermore, the
004
102
110

Ni0.85Se/Ni2P-composite thin films and Co0.85Se/Ni0.85Se-nano- Ni

201
103

202

composites on FTO glass were also prepared by chemical vapor JCPDS No. 18-0888 Ni
deposition10 and co-electrodeposition,11 respectively. However, Ni

10 20 30 40 50 60 70 80 1 2 3 4 5 6 7 8 9 10
the controllable syntheses of Ni0.85Se crystals with different Energy/keV
2θ /degree
sizes or morphologies, and their applications in chemical
catalysis, are very limited.
Herein, the Ni0.85Se crystals with plate-like and particle
shapes were prepared by two-step and one-step hydrothermal
methods, respectively. First, the plate-like Ni-precursor nano-
structures (NSs) were synthesized by mixing 20 mL (0.2 M) of
NiCl2¢6H2O solution and 20 mL (0.2 M) of NaOH solution in a
beaker. After magnetic stirring for 30 min, the mixture was
transferred to a Teflon-lined stainless-steel autoclave with a
capacity of 50 mL, and kept at 180 °C for 12 h; then, plate-like
Ni-precursor NSs were prepared. Second, for the formation of
Ni0.85Se plate-like nanostructures (PNSs), 0.1 g of the above Ni- Figure 1. XRD pattern (a), EDX spectrum (b), SEM image (c),
precursor NSs with plate-like shapes were dispersed in 40 mL of and TEM image (d) (inset is the HRTEM image) of Ni0.85Se PNSs.

Chem. Lett. 2015, 44, 521–523 | doi:10.1246/cl.141139 © 2015 The Chemical Society of Japan | 521
nanostructured hexagonal type Ni0.85Se (JCPDS, No. 18-0888). a 3.0
b 3.0

Absorbance (arb unit)

Absorbance (arb unit)
0 min 0 min
Furthermore, the energy-dispersive X-ray spectroscopy (EDX) 2.5 2 min 2.5 2 min
4 min
4 min
and X-ray photoelectron spectra (XPS) were used to examine the 2.0
.
2.0 .
. .
1.5 1.5
composition of the as-obtained Ni0.85Se PNSs on their near- . .
1.0 18 min 1.0 26 min
surface. EDX result (Figure 1b) shows that the Ni/Se atomic 20 min 28 min
0.5 0.5 30 min
ratio was about 45.4:54.6 (namely, 0.832:1). This result was 22 min
0.0
very close to the Ni/Se atomic ratio (0.85:1) from the XRD
0.0
300 400 500 600 300 400 500 600
Wavelength/nm Wavelength/nm
result (Figure 1a). XPS spectra of the as-obtained Ni0.85Se PNS
samples are shown in Figures S2a­S2c; the Ni2p spectrum c 1.0 d 100

(Figure S2b) could be best fitted with two spin­orbit doublets,

Conversion/%
0.8 80

characteristic of Ni2+ and Ni3+, and two shake-up satellites 0.6 60

C t /C 0
(identified as “Sat.”), by using a Gaussian fitting method.12 The 0.4 II 40
I
binding energy of ca. 55.0 eV was close to the value for Se3d 0.2 20
(Figure S2c).13 According to the XPS analysis, the near-surface 0.0 0
of the sample had a composition of Ni2+, Ni3+, and Se2¹, 0 4 8 12
Time/min
16 20 24 28 32 0 1 2 3
Cycle numbers
4 5

which was in good agreement with the Ni0.85Se. Based on the

XRD, EDX, and XPS results, the sample was almost simply
constituted by Ni0.85Se.
The morphologies and structures of the Ni0.85Se NSs with
different shapes were characterized by the FESEM, trans-
mission electron microscopy (TEM), and high-resolution TEM
(HRTEM) measurements. Figure 1c shows the representative
FESEM image of the sample; the Ni0.85Se sample completely
maintained the plate-like morphology, and the average diameter
over the whole sample was 150­350 nm (Figure S2d). TEM
image of the PNSs is shown in Figure 1d, which was in
accordance with the results from FESEM. HRTEM measurement
was also employed to characterize the as-synthesized Ni0.85Se.
Apparently, the lattice fringe (ca. 0.269 nm) shown in Figure 1d
(right down inset image) was indexed to the (101) crystal planes
of the hexagonal phase, which further confirmed the formation
of Ni0.85Se. Additionally, the hexagonal phase Ni0.85Se nano-
particles (Figure 2 and Figure S3) were also obtained by using
a similar synthesis process as Ni0.85Se PNSs, where only the
NiCl2¢6H2O was used instead of Ni-precursors.
Recently, direct catalytic reduction of 4-NP to 4-AP by
NaBH4 was considered as an important model reaction for
investigating the catalytic activities of nanomaterials.13a,14­27
Here, the catalytic performances of the as-prepared Ni0.85Se
NSs were also investigated for the reduction of 4-NP in the
presence of NaBH4. When the NaBH4 solution was mixed with
the 4-NP solution, the absorption peak shifted from ca. 317 to
ca. 400 nm,13a,14­18 and then, the intensity of the absorption peak
at ca. 400 nm gradually decreased with the addition of Ni0.85Se
NS catalysts. Typical UV­vis absorption spectra of the mixed
solution after reacting for various times are shown in Figure 3.
After ca. 22 min (Figure 3a), the peak at 400 nm almost
disappeared, indicating that the as-obtained Ni0.85Se PNSs
b
Intensity (arb unit)
Figure 3. Time-dependent UV­vis absorption spectra and the
concentration­time curves for reducing 4-NP into 4-AP by
Ni0.85Se NSs with plate-like (a, cI) and particle (b, cII) shapes
as catalysts; (d) conversion of 4-NP in five successive cycles of
reduction with Ni0.85Se PNSs catalyst. Conditions: [4-NP] =
0.25 mM; Ni0.85Se NSs catalysts, 0.1 mg mL¹1; [NaBH4] =
0.02 M; temperature, ca. 25 °C.
showed a good catalytic capacity for the reduction of 4-NP to
4-AP by NaBH4. The conversion of 4-NP into 4-AP took
ca. 30 min when the same quality of Ni0.85Se nanoparticles
(Figure 3b) were used as catalysts, which was lower than that
of the Ni0.85Se PNSs (Figure 3a). More interestingly, by using
Ni0.85Se PNSs as catalyst, no induction time (IT) existed in the
reduction process (Figure 3cI). However, the IT was more than
6 min (Figures 3cII and S4) in the presence of Ni0.85Se nano-
particles as catalyst. Compared to some previous reports
(Table 1), the Ni0.85Se PNSs also showed better catalytic activity
for the reduction of 4-NP. If we assumed that the rate of
adsorption of 4-NP on the surface of a catalyst was the pre-
dominant factor in the induction period, the adsorption of 4-NP
might play an important role in activating the reaction.13a,14b,15,16
Here, the specific surface area and the BJH pore diameter
(Table S1) were 18.2 m2 g¹1 and 21.5 nm for Ni0.85Se PNSs
(Figure S5a), 24.7 m2 g¹1 and 14.8 nm for Ni0.85Se nanoparticles
(Figure S5b), respectively. Although the Ni0.85Se nanoparticles
(24.7 m2 g¹1) had the bigger specific surface area than Ni0.85Se
PNSs (18.2 m2 g¹1), the BJH pore diameter of Ni0.85Se nano-
particles (14.8 nm) was smaller than Ni0.85Se PNSs (21.5 nm).
Nitrogen adsorption and desorption measurements (Figure S5)
showed that the pores in the Ni0.85Se PNSs should come from
the holes in the plate-like structures (Figure S5a), and the pores
in the Ni0.85Se nanoparticles should come from the crevices in
aggregation (Figure S5b) particles. The considerable enhance-

ment in catalytic activity for the Ni0.85Se PNSs could probably

101

be attributed to the following reasons: (i) the walls of the PNSs

102
110

could provide more active sites than Ni0.85Se nanoparticles

201
103

202

due to their shapes;14c,19,26 (ii) the PNSs could provide more

JCPDS No. 18-0888
catalytic channels on their surfaces than Ni0.85Se nanoparticles
10 20 30 40 50 60 70 80 to simultaneously accommodate both the oxidation and the
2θ /degree reduction half reactions;14c,15 (iii) the plate-like structures could
improve the electron-transfer rate than the particle structures on
Figure 2. SEM image (a) and XRD pattern (b) of Ni0.85Se their surfaces for 4-NP reduction.14c,16,19,26 As an example, the
nanoparticles. reusability experiments for the Ni0.85Se PNSs were performed,

522 | Chem. Lett. 2015, 44, 521–523 | doi:10.1246/cl.141139 © 2015 The Chemical Society of Japan
 Table 1. Comparison of the catalytic reduction of 4-NP to 4-AP by using different micro-/nanomaterials as catalysts
Initial concentrations Catalyst amount Reaction Induction Reaction
Type of catalysts Ref
of 4-NP/mM /mg mL¹1 temperature/°C time/s time/min
Ni0.85Se PNSs 0.25 0.033 25 0 22 This work
Ni0.85Se nanoparticles 0.25 0.033 25 360 24 This work
FeNi2 spheres 0.1 0.033 20 0 60 14a
Ni33.8Co66.2 dendrites 0.1 0.033 20 100 30 14b
Flower-like Ni33.4Co66.6 0.1 0.033 20 120 35 14b
Au nanoboxes 0.14 ® 24 120 2 16
Au partially hollow nanoboxes 0.14 ® 24 90 5 16
Dendritic Pt 0.1 ® ® 0 100 20
Pt­Au ANCs 0.01 0.04 ® 0 33 27a
Microgel­Pd 0.1 ® 20 0 30 27b

and it was found that the present catalyst could be recycled by
centrifugation and repeated washing. As shown in Figure 3d, the
conversion rate of 4-NP to 4-AP decreases as the cycle-index
increases. Obviously, the conversion rate was only 25% for
Ni0.85Se PNSs at the end of the 5th cycle, while keeping the
reaction time of ca. 22 min unchanged. The primary reason for
low conversion rates was that the catalysts might adhere to
the surface of the magneton and the wall of the beaker during
the recovery process. As a consequence, the metal chalcogenide
catalyst with magnetic separation capability for recyclable
utilization should be the research hotspot in the future.
In summary, we have developed a facile and efficient self-
templating conversion method to synthesize Ni0.85Se plate-like
nanostructures. After a mild selenylation process with fresh
NaHSe, the solid plate-like Ni-precursors could be chemically
transformed into corresponding nickel selenides. Furthermore,
the Ni0.85Se nanoparticles were obtained by using NiCl2¢6H2O
as the nickel source. The as-prepared Ni0.85Se crystals exhibited
higher catalytic activity for 4-nitrophenol reduction than the
Ni0.85Se particle nanostructures. Specifically, these Ni0.85Se
plate-like nanostructures could deliver remarkable catalytic
performance with a reaction time of ca. 22 min. It is found that
metal selenides showed good catalytic property for the hydro-
genation of 4-nitrophenol and are believed to be a candidate
for next-generation catalysts for the reduction of other nitro
compounds.
This work was financially supported by the National Natural
Science Foundation of China (Nos. 21071005, 21271006,
21471007, and 21401004), and the Research Culture Funds
(Nos. 2011rcpy038 and 2014xmpy13) and Innovation Funds
(No. 2014cxjj13) of Anhui Normal University.
Supporting Information is available electronically on J-STAGE.
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