Supporting information
Co1.29Ni1.71O4-Co3S4-Co3O4 Ternary Nanocomposites: Synthesis and Their Superior Performances for
Hydrogenation of p-Nitrophenol and Adsorption for Methyl Blue
Fang-Yuan Wang, Yan-Ling Fan, Jing-Jing Ni, Ting-Ting Xu, Ji-Ming Song*
The Key Laboratory of Environment Friendly Polymer Materials of Anhui Province, School of Chemistry & Chemical
Engineering, Anhui University, Hefei, Anhui, 230601, P. R. China.
Tel:+86 0551 63861279 : Fax: +86 0551 63861279
E-mail: jiming@ahu.edu.cn
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1. Materials
Cobalt chloride hexahydrate (CoCl26H2O), nickel chloride hexahydrate (NiCl26H2O), sodium borohydride
(NaBH4, 96%, wt%), sodium thiosulfate (Na2S2O35H2O), pH=9 buffer solution of NH4Cl/NH3H2O,
p-nitrophenol (4-NP), methyl blue (MB), polyvinylpyrrolidone (PVP), hexadecyltrimethylammonium
bromide (CTAB), sodium dodecyl sulfonate (SDS), sodium dodecyl benzene sulfonate (SDBS). All the
reagents were analytic grade and used as received without further purification.
2. Characterization
The phase structural information of the samples was collected by X-ray powder diffraction (XRD)
measurements that were carried out on a Rigaku D/max-RA X-ray diffract meter (Cu K radiation，
=0.15406 nm) with 2 value from 10o to 80o at a scanning rate of 4o min-1. The morphology of the samples
was analyzed by scanning electron microscopy (SEM，Hitachi S-4800，operating at 5.0 kV) and transmission
electron microscopy (TEM，Hitachi
JEM-2100 instruments with an acceleration voltage of 200 kV).
Inductively coupled plasma atomic emission spectrometry (ICP-AES) measurements were measured by
using VarioELⅢ (Elementar Analysensyteme Gmbh，Germany). The specific surface area was calculated
by using the Brunauer-Emmett-Teller (BET) method. In addition, the UV-Vis measurements were performed
on an Agilent 8453 ultraviolet visible spectrophotometer. The X-ray photoelectron spectra (XPS) were taken
on an ESCALab MKII X-ray photoelectron spectrometer to obtain further evidence for the purity and
composition of the as-prepared samples.
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80
Pore Volume (cm 3g-1 nm -1 )
Quantity Adsorbed (cm2  g STP)
0.0018
100
0 C
10C
20C
0.0016
0.0014
0.0012
0.0010
0.0008
0.0006
0.0004
0
20
40
60
80
100 120 140 160 180
Pore diameter (nm)
60
40
20
0
0.0
0.2
0.4
0.6
0.8
1.0
Relative Pressure (P  P0)
Fig. S1 Nitrogen adsorption-desorption isotherms and pore size distribution curves (inset) of the as-prepared samples.
In order to understand the Co1.29Ni1.71O4-Co3S4-Co3O4 nanocomposites, the Brunauer-Emmett-Teller
(BET) surface area was determined as 19.80 m2 g-1 (Fig. S1, black line). The result of BJH
(Barrett-Joyner-Halenda) desorption pore distribution (inset in Fig. S1) indicates that the as-prepared
Co1.29Ni1.71O4-Co3S4-Co3O4 nanocomposites possess a pore size distribution from 7 to 175 nm, revealing
that the pores are mainly mesoporous and macroporous. The large BET surface area of the sample is
beneficial to its catalytic and adsorption behavior. The specific surface areas of the nanocomposites obtained
at 10 oC, and 20 oC have been also displayed (Fig. S1, red line and green line). Their values are 16.44, and
13.90 m2 g-1, respectively. The BET surface areas decreased when the reaction temperature increased. We
thought that the low reaction temperature was beneficial to the formation of wrinkles for nanocomposite.
Because the thickness of wrinkles is very thin, the move rate of ions in aqueous solution will increase when
the reaction temperature rises, thus can destroy the ambient environment of forming wrinkles.
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Fig. S2 SEM images of samples synthesized at different temperatures: (a) 0 oC, (b) 10 oC, (c) 20 oC.
a
b
400 nm
200 nm
c
d
Fig. S3 The samples prepared without Na2S2O3.5H2O: (a) and (b) SEM images, (c) and (d) TEM images.
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a
b
PVP
200 nm
c
CTAB
200 nm
d
SDS
SDBS
200 nm
200 nm
Fig.S4 SEM images of the samples prepared at different surfactants: (a) 0.3 g PVP, (b) 0.3 g CTAB, (c) 0.3 g SDS, (d) 0.3 g
SDBS.
As everyone knows, the kinds of surfactants can directly influence the morphology and structure of the
product during synthesis process. PVP, CTAB, SDS, SDBS are very common laboratory surfactants.
Although our experiment did not use surfactants, we still explored the effects of surfactants on the final
samples in this experiment. Figure S4 shows the SEM images of the as-prepared samples with different
surfactants while the other conditions being the same. We can clearly see that the morphology of the
obtained samples have not greatly changed in the condition of 0.3 g PVP. Since adding PVP did not make no
differences on the as-prepared samples morphology, there is no necessary to add PVP in the experiment. To
figure out the effect of other surfactants in this experiment, investigations have been done by replacing PVP
with different surfactants, such as CTAB, SDS and SDBS. As shown in Figure S4b, S4c and S4d, when
other surfactants were used to participate in the reaction process, the wrinkle nanofilms disappeared and the
samples reunite together. Thus, CTAB, SBS and SDBS are not suitable for the synthesis of cobalt-nickel
oxide nanocomposites in the present synthesis.
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a
Intensity (a.u.)
b
o
with Na2S2O3 800 C
o
with Na2S2O3 500 C
400 nm
10
20
30
40
50
60
70
80
2 (degree)
Fig. S5 (a) XRD pattern of the samples calcined at 800 oC, (b) SEM image of samples calcined at 800 oC.
Calcination temperature is also an important factor to influence the crystallinity and the morphology of the
final samples. The samples were calcined at 800 oC. Comparing with the XRD pattern at 500 oC, we can see
that the location of diffraction peaks did not change at 800 oC, which indicated the phase of the final
products unchanged (Fig. S5). The crystailinity improvedd when the calcination temperature increased.
However, the structure and the morphology changed greatly. The wrinkles disappeared entirely.
a
b
0.075
0.090
kapp (s-1)
kapp (s-1)
0.060
0.045
0.075
0.060
0.030
0.045
0.015
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
Mass (mg)
C (mol/L)
Fig. S6 UV-vis absorption spectra: (a) the plot of kapp versus the concentration of NaBH4, (b) the plot of kapp versus catalyst
dose.
To find out the most appropriate concentration of NaBH4, we record the catalytic reaction under the
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different concentrations of NaBH4 from 0.025 mol L-1 to 0.15 mol L-1 (Fig. S6a). According to Lambert–
Beer law: A=bc
(1)
Where A is the absorbance of p-nitrophenol,  (L mol-1 cm-1) is the molar extinction coefficient, b is the path
length of the spectrophotometer cell (1cm), and c (mol L-1) is the concentration of p-nitrophenol. The kinetic
equation for the hydrogenation of p-nitrophenol is expressed as ln(Ct/C0) = ln(At/A0) = -kt. The value of
Ct/C0 is measured from the ratio of At/A0, then the apparent rate constant (kapp) is obtained from the linearly
fitted slope of ln(Ct/C0)-t. Each concentration can get a kapp value (Fig. S6a). We found that the reaction rate
increased with the increase of BH4- concentration in the range 0-0.075 M, while it remained constant in the
range of 0.075-0.15 M. Thus, we chose 0.075 M of NaBH4 as experimental concentration. From the Fig. S6a,
we can see that the kapp was 4.20 min-1 in the concentration of NaBH4=0.075 M, 4-NP=4 mmol L-1 and 1.5
mg catalysts. Besides, the dosage of as-synthesized ternary nanocomposites was investigated for the
catalytic efficiency as well. The catalytic performance was improved with increasing the dosage of samples.
Fig. S6b displayed that the rate constant increased from 2.83 min-1 to 5.32 min-1 with increasing dosage of
samples from 1 mg to 2.5 mg. So increasing dose of catalysts would be beneficial to the reduction reaction
of 4-NP.
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