Junxing Han et al.
COMMUNICATIONS
Quantitative calculations of liquid products were performed
using the internal standard method. The reactions for other
vegetable oils were performed accordingly.
Preparative Procedure for the Mo2C/AC Catalyst
Mo2C/AC catalyst was prepared by the carbothermal hydro-
gen reduction (CHR) method with some modifications. Pu-
rification of activated charcoal (AC) was carried out by
mixing pristine AC (4 g, surface area 1189 m2 gÀ1) with 6M
HNO3 (100 mL) at 808C for 3 h. After filtration, the sample
was washed and dried at 1208C overnight. Then purified AC
(2 g) was mixed with ammonium molybdate (0.7 g,
0.57 mmol) and deionized water (15 mL) in a 100-mL
round-bottom flask. The mixture was sonicated at 120 W for
1.5 h, and then water was removed using a rotatory evapora-
tor. The obtained sample was dried at 1208C for 12 h. The
dried sample was then carburized in a H2 flow following a
three-step heating ramp: from room temperature to 4508C
at 58C minÀ1, and then to 7008C at 18C minÀ1 and then
maintained at 7008C for 2 h. Prior to exposure to air, the as-
prepared Mo2C/AC catalyst was passivated in a flow of 1%
O2/N2 for 12 h at ambient temperature. The theoretical
Mo2C loading was approximately 20% based on AC sup-
port.
Using PdNP/BaSO4 as catalyst: In a typical procedure
for model compounds (Table 2), methyl palmitate (0.50 g),
PdNP/BaSO4 catalyst (0.20 g) and hexane (15 mL) were
added to a 100-mL stainless steel autoclave. The reaction
system was pressured with hydrogen to 1.0 MPa and heated
to react at 2808C for 5.0 h. After the reaction, gas and liquid
products were collected and then detected by gas chroma-
tography (GC) and GC-MS, respectively. Quantitative calcu-
lations of liquid products were performed using the internal
standard method. The reactions for other substrates were
performed accordingly.
Acknowledgements
This work was supported by the National Science Foundation
of China (21073160 and J0830413), the National Basic Re-
search Program of China (2007CB210204) and the Top Key
Discipline of Zhejiang Province.
Deoxygenation Reactions
Using unsupported Mo2C as catalyst: In a typical procedure
for model compounds (Table 1), methyl stearate (0.5 g), un-
supported Mo2C catalyst (1.0 g) and hexane (15 mL) were References
added to a 100-mL stainless steel autoclave. The reaction
system was pressured with hydrogen to 1.4 MPa and heated
to react at 2808C for 5.0 h. After the reaction, gas and liquid
products were collected and then detected by gas chroma-
tography (GC) and GC-MS, respectively. Quantitative calcu-
lations of liquid products were performed using the internal
standard method. The reaction for stearic acid was per-
formed accordingly.
In a typical procedure for renewable oils (Table 3), olive
oil (0.35 g), unsupported Mo2C catalyst (1.0 g) and hexane
(15 mL) were added to a 100-mL stainless steel autoclave.
The reaction system was pressured with hydrogen to
2.0 MPa and heated to react at 3008C for 4.0 h. After the re-
action, gas and liquid products were collected and then de-
tected by gas chromatography (GC), HPLC and GC-MS, re-
spectively. Quantitative calculations of liquid products were
performed using the internal standard method. The reaction
for sunflower oil was performed accordingly.
Using Mo2C/AC as catalyst: In a typical procedure for
model compounds (Table 1 and Table 2), methyl stearate
(0.50 g), Mo2C/AC catalyst (0.20 g) and hexane (15 mL)
were added to a 100-mL stainless steel autoclave. The reac-
tion system was pressured with hydrogen to 1.0 MPa and
heated to react at 2808C for 4.0 h. After the reaction, gas
and liquid products were collected and then detected by gas
chromatography (GC) and GC-MS, respectively. Quantita-
tive calculations of liquid products were performed using
the internal standard method. The reactions for other sub-
strates were performed accordingly.
In a typical procedure for renewable oils (Table 3), olive
oil (0.45 g), Mo2C/AC catalyst (0.25 g) and hexane (15 mL)
were added to a 100-mL stainless steel autoclave. The reac-
tion system was pressured with hydrogen to 1.5 MPa and
heated to react at 2808C for 4.0 h. After the reaction, gas
and liquid products were collected and then detected by gas
chromatography (GC), HPLC and GC-MS, respectively.
[1] G. W. Huber, S. Iborra, A. Corma, Chem. Rev. 2006,
106, 4044–4098.
[2] A. Corma, S. Iborra, A. Velty, Chem. Rev. 2007, 107,
2411–2502.
[3] P. T. Anastas, M. M. Kirchhoff, Acc. Chem. Res. 2002,
35, 686–694.
[4] S. Lestari, P. Mꢃki-Arvela, J. Beltramini, G. Q. M. Lu,
D. Yu. Murzin, ChemSusChem 2009, 2, 1109–1119.
[5] G. W. Huber, P. O. Connor, A. Corma, Appl. Catal. A
2007, 329, 120–129.
ˇ
[6] a) M. Snꢄre, I. Kubickovꢅ, P. Mꢃki-Arvela, D. Chicho-
va, K. Erꢃnen, D. Yu. Murzin, Fuel 2008, 87, 933–945;
ˇ
b) M. Snꢄre, I. Kubickovꢅ, P. Mꢃki-Arvela, K. Erꢃnen,
D. Yu. Murzin, Ind. Eng. Chem. Res. 2006, 45, 5708–
5715; c) I. Simakova, O. Simakova, P. Mꢃki-Arvela, D.
Yu. Murzin, Catal. Today 2010, 150, 28–31; d) I. Sima-
kova, O. Simakova, P. Mꢃki-Arvela, A. Simakov, M.
Estrada, D. Yu. Murzin, Appl. Catal. A 2009, 355, 100–
108.
[7] J. X. Han, H. Sun, Y. Q. Ding, H. Lou, X. M. Zheng,
Green Chem. 2010, 12, 463–467.
[8] K. Murata, Y. Liu, M. Inaba, I. Takahara, Energy Fuels
2010, 24, 2404–2409.
[9] J. Fu, X. Y. Lu, P. E. Savage, Energy Environ. Sci. 2010,
3, 311–317.
[10] J. X. Han, H. Sun, J. Z. Duan, Y. Q. Ding, H. Lou,
X. M. Zheng, Adv. Synth. Catal. 2010, 352, 1805–1809.
[11] R. B. Levy, M. Boudart, Science 1973, 181, 547–549.
[12] N. Ji, T. Zhang, M. Y. Zheng, A. Q. Wang, H. Wang,
X. D. Wang, J. G. Chen, Angew. Chem. 2008, 120, 8638–
8641; Angew. Chem. Int. Ed. 2008, 47, 8510–8513.
[13] S. J. Peppernick, K. D. D. Gunaratne, A. W. Castleman
Jr, Proc. Natl. Acad. Sci. USA 2010, 107, 975–980.
[14] T. Hyeon, M. M. Fang, K. S. Suslick, J. Am. Chem. Soc.
1996, 118, 5492–5493.
2582
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 2577 – 2583