Wang et al.
FULL PAPER
Table 3 Catalytic data of various catalysts in the aerobic oxidation of glycerola
OH
OH
HO
OH
HO
OH
O
O
O
Catalyat, O2
H2O, NaOH
OH
glyceric acid (GLYA) tartronic acid (TARAC)
HO
OH
O
glycerol
OH
HO
OH
O
HO
OH
OH
O
O
O
hydroxypyruvic acid (HPYA)
glycolic acid (GLYCA)
oxalic acid (OXALA)
Product selectivity/%
Entry
Catalyst
Conversion/%
GLYA
TARAC
12.3
HPYA
0.0
GLYCA
9.3
OXALA
10.5
Othersb
16.2
1
2
3
0.9% Pd/MAO
0.7% Au/MAO
18.6
85.2
98.5
49.9
66.2
43.0
10.0
8.4
5.8
4.6
5.0
0.7% Au-0.9% Pd/MAO
36.6
3.2
5.6
0.4
11.2
a Reaction conditions: 3 mmol of glycerol, 0.2 MPa of O2, 10 mL of water, 12 mmol of NaOH, molar ratio of glycerol with metal (Au and
Pd) at 2000 under the temperature of 323 K for 2 h; b The by-products are dihydroxyacetone, glyoxylic acid, CO2, formic acid, and others.
References
acid (HPYA), glycolic acid (GLYCA), and oxalic acid
(OXALA). Notably, 0.9% Pd/MAO catalyst shows low
conversion (18.6%) and GLYA selectivity (49.9%, Ta-
ble 3, Entry 1). However, 0.7% Au/MAO exhibits rela-
tively high glycerol conversion (85.2%) and GLYA se-
lectivity (66.2%, Table 3, Entry 2). These data are
comparable with those of Au nanoparticles reported
previously.[41] Interestingly, 0.7% Au-0.9% Pd/MAO
catalyst exhibits very high conversion of glycerol, giv-
ing at 98.5%. In addition, relatively high selectivity for
TARAC is obtained (36.6%, Table 3, Entry 3). This is
quite different from the results in literature that GLYA
was usually the major product with extremely low yield
of TARAC in glycerol oxidation on Au, Au-Pd and
Au-Pt catalyst.[4,27,33,34,36] Because TARAC is converted
from further oxidation of GLYA, the high selectivity for
TARAC is to suggest that 0.7% Au-0.9% Pd/MAO
catalyst is very active.
[1] Hutchings, G. J. J. Catal. 1985, 96, 292.
[2] Haruta, M.; Koboyashi, T.; Sano, H.; Yamada, N. Catal. Lett. 1987,
16, 405.
[3] Herzing, A. A.; Kiely, C. J.; Carley, A. F.; Landon, P.; Hutchings, G.
J. Science 2008, 321, 1331.
[4] Villa, A.; Veith, G. M.; Prati, L. Angew. Chem., Int. Ed. 2010, 49,
4499.
[5] (a) Ren, N.; Yang, Y. H.; Zhang, Y. H.; Wang, Q. R.; Tang, Y. J.
Catal. 2007, 246, 215; (b) Wang, L.; Zhang, W.; Su, D.; Meng, X.;
Xiao, F.-S. Chem. Commun. 2012, 48, 5476.
[6] Abad, A.; Concepcion, P.; Corma, A.; Garcia, H. Angew. Chem., Int.
Ed. 2005, 44, 4066.
[7] (a) Zhang, X.; Shi, H.; Xu, B.-Q. J. Catal. 2011, 279, 75; (b) Wang,
L.; Meng, X.; Xiao, F.-S. Chin. J. Catal. 2010, 31, 943.
[8] Wang, L.; Wang, H.; Hapala, P.; Zhu, L.; Ren, L.; Meng, X.; Lewis,
J. P.; Xiao, F.-S. J. Catal. 2011, 281, 30.
[9] Su, F.-Z.; Liu, Y.-M.; Wang, L.-C.; Cao, Y.; He, H.-Y.; Fan, K.-N.
Angew. Chem., Int. Ed. 2008, 47, 334.
[10] Zhang, X.; Shi, H.; Xu, B.-Q. Angew. Chem., Int. Ed. 2005, 44,
7132.
[11] Mori, K.; Hara, T.; Mizugaki, T.; Ebitani, K.; Kaneda, K. J. Am.
Chem. Soc. 2004, 126, 10657.
Conclusions
In summary, we have successfully designed and
prepared bimetallic Au-Pd nanoparticles with rich edge
and corner sites on MAO support (0.7% Au-0.9%
Pd/MAO). This catalyst gives superior activities for the
aerobic oxidation of benzyl alcohol to benzaldehyde.
Very interestingly, this catalyst exhibits both high con-
version of glycerol and high TARAC selectivity in the
aerobic oxidation of glycerol. These results would be
potentially important to develop of new catalysts for the
production of fine chemicals.
[12] Zhao, R.; Ji, D.; Lv, G. M.; Qian, G.; Yan, L.; Wang, X. L.; Suo, J.
S. Chem. Commun. 2004, 904.
[13] Ma, C. Y.; Mu, Z.; Li, J. J.; Jin, Y. G.; Cheng, J.; Lu, G. Q.; Hao, Z.
P.; Qiao, S. Z. J. Am. Chem. Soc. 2010, 132, 2608.
[14] Yan, W.; Brown, S.; Pan, Z.; Mahurin, S. M.; Overbury, S. H.; Dai,
S. Angew. Chem., Int. Ed. 2006, 45, 3614.
[15] Zope, B. N.; Hibbitts, D. D.; Neurock, M.; Davis, R. J. Science 2010,
330, 74.
[16] Chen, M. S.; Kumar, D.; Yi, C. W.; Goodman, D. W. Science 2005,
310, 291.
[17] Wang, L.; Meng, X. J.; Wang, B.; Chi, W. Y.; Xiao, F.-S. Chem.
Commun. 2010, 46, 5003.
[18] Zhang, Q. H.; Deng, W. P.; Wang, Y. Chem. Commun. 2011, 47,
9275.
Acknowledgement
[19] Chen, Z.; Cui, Z.-M.; Fang, N.; Jiang, L.; Song, W.-G. Chem.
Commun. 2010, 46, 6524.
[20] Wang, L.; Meng, X.; Xiao, F.-S. Chin. J. Catal. 2010, 31, 943.
[21] Min, B. K.; Friend, C. M. Chem. Rev. 2007, 107, 2709.
[22] (a) Okumura, M.; Kitagawa, Y.; Haruta, M.; Yamaguhi, K. Chem.
This work is supported by the National Natural Sci-
ence Foundation of China (20973079 and U1162201)
and the State Basic Research Project of China
(2009CB623501).
8
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, XX, 1—9