Palladium, Gold and Gold-palladium Nanoparticle Supported Carbon Materials for
Cyclohexane Oxidation
VISHAL J. MAYANI, SURANJANA V. MAYANI AND SANG WOOK KIM*
Department of Advanced Materials Chemistry, College of Science and Technology,
Dongguk University, Gyeongju, Gyeongbuk 780-714, Republic of Korea,
Email: swkim@dongguk.ac.kr, Tel: +82-54-770-2216, Fax: +82-54-770-2386
Synthesis of Nano Silica Ball (NSB-25/170). Nano silica ball (NSB) was prepared by hydrolysis
and condensation of TEOS. Here, we have synthesized two sets of NSB (25 and 170 nm). In a
typical synthesis of NSB-25, 10 mL distilled water and 7.8 mL of TEOS were stirred (450 rpm)
in 500 mL of absolute ethanol (EtOH) for 30 min. 4 mL of NH4OH (28 wt %) was added to the
resulting mixture, which was left to stir for further 24 h at room temperature at 450 rpm. The
reaction mixture was transferred to oven and heated at 70 °C until complete dryness. The solid
product was washed (ethanol and warm water) and dried at room temperature in air. The resulted
NSB-25 was calcined at 550 °C for 6 h. For NSB-170, 10.5 mL distilled water and 30 mL of
TEOS were stirred in 500 mL of ethanol (EtOH) for 30 min. 14 mL of NH4OH (28 wt %) was
added to the resulting mixture, which was left to stir for further 4-5 h at room temperature at 450
rpm. The reaction mixture was transferred to oven and heated at 70 °C until complete dryness.
The solid product was washed (ethanol and warm water) and dried at room temperature in air.
The resulted NSB-170 was calcined at 550 °C for 6 h. (NSB-25); yield (2.3 g), BET Surface area
of NSB-25: 30 m2/g, FTIR (KBr) 811, 1104, 1627, 1870, 3439, 3746 cm-1. (NSB-170); yield (6.1
g), FTIR (KBr) 469, 553, 799, 949, 1096, 1396, 1632, 3430 cm-1, BET Surface area of NSB-170:
163 m2/g (Mayani et al., 2012 a).
Synthesis of Carbon Cage (CC-25/170). The pitch residue, used as a carbon cage precursor,
was prepared according to the method reported previously under a heat extraction and selfcrystallization method (Mayani et al., 2011). For a typical procedure, 12 g of pitch was heated at
50 °C and mixed homogeneously with 10 g of NSB-25/NSB-170 in crucible for 10 min. After
cooling to room temperature, the mixture was carbonized at 900 °C for 4 h under nitrogen
atmosphere to produce the carbon silica composite (CSC-25/170) material. The resulting CSC25/170 material was treated with 10 % hydrofluoric acid (HF) for 12 h. The solid carbon cage
(CC-25/170) material was washed with distilled water and followed by drying at 100 °C in oven
(Scheme 1). (CC-25); yield (6.3 g), BET Surface area of CC-25: 82 m2/g, FTIR (KBr) 1113,
1584, 1620, 3437 cm-1. Elemental analysis results showed that CC-25 contained > 94 wt %
carbon and < 1.2 wt % H after carbonization at > 900 °C. (CC-170); yield (6.2 g), BET Surface
area of CC-170: 212 m2/g, FTIR (KBr) 811, 1099, 1257, 1602, 3453 cm-1. Elemental analysis
results showed that CC-170 contained > 95 wt % carbon and < 0.4 wt % H after carbonization at
> 900 °C (Mayani et al., 2012 b).
Characterization. The synthesized palladium and gold-palladium incorporated carbon
nanocomposites were fully characterized by microanalysis, N2 adsorption–desorption isotherm,
SEM–EDS, TEM, ICP, TGA, and PXRD (Figures S1 to S11).
Relative Intensity (a.u.)
(e)
(d)
(c)
(b)
(a)
0
2
4
6
8
10
2 theta (Degrees)
Figure S1. Low-angle PXRD patterns of NSB-25 (a), CC-25 (b), CGC-25 (c), CPC-25 (d) and
CGPC-25 (e).
Relative Intensity (a.u.)
(t)
(s)
(r)
(q)
(p)
0
2
4
6
8
10
2 theta (Degrees)
Figure S2. Low-angle PXRD patterns of NSB-170 (p), CC-170 (q), CGC-170 (r), CPC-170 (s)
and CGPC-170 (t).
Relative Intensity (a.u.)
(E)
(D)
(C)
(B)
(A)
10
20
30
40
50
60
70
80
2 theta (Degrees)
Figure S3. Wide-angle PXRD patterns of NSB-25 (A), CC-25 (B), CGC-25 (C), CPC-25 (D)
and CGPC-25 (E).
Relative Intensity (a.u.)
(T)
(S)
(R)
(Q)
(P)
10
20
30
40
50
60
70
80
2 theta (Degrees)
Figure S4. Wide-angle PXRD patterns of NSB-170 (P), CC-170 (Q), CGC-170 (R), CPC-170
(S) and CGPC-170 (T).
Figure S5. SEM images of NSB-25 (A), CC-25 (B), CGC-25 (C), CPC-25 (D) and CGPC-25
(E).
Figure S6. SEM images of NSB-170 (a), CC-170 (b), CGC-170 (c), CPC-170 (d) and CGPC170 (e).
Figure S7. TEM images of NSB-25 (A), CC-25 (B), CGC-25 (C), CPC-25 (D) and CGPC-25
(E and F).
Figure S8. TEM images of NSB-170 (a), CC-170 (b), CGC-170 (c), CPC-170 (d) and CGPC170 (e).
200
140
120
Volume Adsorbed
160
140
120
Volume Adsorbed
180
100
80
60
40
20
100
0
0.0
80
NSB-25
0.2
0.4
0.6
0.8
1.0
Relative Pressure (P/Po)
60
40
20
NSB-170
0
0.0
0.2
0.4
0.6
0.8
Relative Pressure (P/Po)
Figure S9. Nitrogen adsorption-desorption isotherms of NSB-25 and NSB-170
1.0
100
% Weight loss
95
90
NSB-25
CC-25
CGC-25
CPC-25
CGPC-25
85
80
0
100
200
300
400
500
600
700
800
900
Temperature/Time
Figure S10. Thermo-gravimetric analysis (TGA) curves of NSB-25, CC-25, CGC-25, CPC-25
and CGPC-25.
100
% Weight loss
95
90
NSB-170
CC-170
CGC-170
CPC-170
CGPC-170
85
80
0
100
200
300
400
500
600
700
800
900
Temperature/Time
Figure S11. Thermo-gravimetric analysis (TGA) curves of NSB-170, CC-170, CGC-170, CPC170 and CGPC-170.
References
Mayani, S. V.; Mayani, V. J.; Park, S. K.; Kim, S. W. (2012 a). Synthesis and characterization
of metal incorporated composite carbon materials from pyrolysis fuel oil, Mater. Lett., 82,
120-123.
Mayani, V. J., Mayani, S. V., Kim, S. W. (2012 b). Development of nanocarbon gold composite
for heterogeneous catalytic oxidation, Mater. Lett, 7, 90-93.
Mayani, V.J., Mayani, S.V., Lee ,Y., Park, S.K. (2011). A non-chromatographic method for the
separation of highly pure naphthalene crystals from pyrolysis fuel oil, Sep. Purif. Technol.,
80, 90-95.