4
1
2
3
4
5
6
7
8
9
0
1
2
3
4
hydrogenation should not be restricted by the pore diffusion
of reactants or products on all these catalysts. Interestingly,
no any byproduct was detected in the final product even
though at the lower conversion of esters. While for the
49 21276186, 21325626, 91434127, 21103224) and the Tianjin
5
5
5
5
0
1
2
3
Natural Science Foundation (13JCZDJC33000).
Supporting
Information
is
available
on
2
2
traditional Ru-based catalyst
and CuO/ZnO/Al
2
O
3
http://dx.doi.org/10.1246/cl.
7
,23
catalyst
reported previously, the formation of some
5
4 References and Notes
byproducts was inevitable as a result of the trans-
esterification reaction. Meanwhile, a higher conversion can
be also achieved for the hydrogenation of Methyl caprylate
55
56
57
1
2
3
4
5
M. A. Sánchez, G. C. Torres, V. A. Mazzieri and C. L. Pieck, J.
Chem. Technol. Biot. 2017, 92, 27.
D. Ren, X. Wan, F. Jin, Z. Song, Y. Liu and Z. Huo, Green Chem.
2016, 18, 5999.
M. A. Sánchez, V. A. Mazzieri, M. A. Vicerich, C. R. Vera and C.
L. Pieck, Ind. Eng. Chem. Res. 2015, 54, 6845.
M. A. Sánchez, V. A. Mazzieri, M. A. Vicerich, C. R. Vera and C.
L. Pieck, J. Chem. 2015, 2015, 1.
Yu-uki Kojima, Shingo Kotani, Makoto Sano, Toshimitsu Suzuki
and a. T. Miyake, Journal of the Japan Prtroleum Insitiute 2013,
56, 133.
T. Miyake, T. Makino, S. I. Taniguchi, H. Watanuki, T. Niki, S.
Shimizu, Y. Kojima and M. Sano, Appl. Catal. A-Gen. 2009, 364,
108.
L. He, H. Cheng, G. Liang, Y. Yu and F. Zhao, Appl. Catal. A-
Gen. 2013, 452, 88.
L. Li, D. Ren, J. Fu, Y. Liu, F. Jin and Z. Huo, J. Energ. Chem.
2016, 25, 507.
P. Yuan, Z. Liu, W. Zhang, H. Sun and S. Liu, Chinese Journal of
Catalysis 2010, 31, 769.
Y. Wang, Y. Zhao, J. Lv and X. Ma, ChemCatChem 2017, 9, 1.
H. Yang, P. Gao, C. Zhang, L. Zhong, X. Li, S. Wang, H. Wang,
W. Wei and Y. Sun, Catal. Commun. 2016, 84, 56.
P. Ai, M. Tan, Y. Ishikuro, Y. Hosoi, G. Yang, Y. Yoneyama and
N. Tsubaki, ChemCatChem 2016, 1067.
S. S. Y. Chui, S. M. F. Lo, J. P. H. Charmant, A. G. Orpen and I.
D. Williams, Science 1999, 283, 1148.
Y. Zhao, Y. Zhang, Y. Wang, J. Zhang, Y. Xu, S. Wang and X.
Ma, Appl. Catal. A-Gen. 2017, 539, 59.
Y. Wang, S. Sang, W. Zhu, L. Gao and G. Xiao, Chem. Eng. J.
2016, 299, 104.
Y. Zhao, S. Li, Y. Wang, B. Shan, J. Zhang, S. Wang and X. Ma,
Chem. Eng. J. 2017, 313, 759.
S. Zhao, H. Yue, Y. Zhao, B. Wang, Y. Geng, J. Lv, S. Wang, J.
Gong and X. Ma, J. Catal. 2013, 297, 142.
Y. Zhao, S. Zhao and Y. Geng, Catal. Today 2016, 276, 28.
H. Niu, S. Liu, Y. Cai, F. Wu and X. Zhao, Microporous
Mesoporous Mater. 2016, 219, 48.
1
1
1
1
1
and Methyl laurate on Cu@C-H
extensive applicability of this catalyst in aliphatic alcohols
synthesis. Therefore, the Cu@C-H catalyst as well as the
2
catalyst, indicating the
5
5
6
6
6
8
9
0
1
2
2
preparation strategy deserve a further study to improve its
catalytic activity.
1
5
Table 2. catalytic performance of Cu@C-H
2
for ester hydrogenation
63
6
6
6
6
4
5
6
7
2
4 h 36 h
6
Reactant
product
butanol
Conv.
Sel.
Conv.
(%)
-
Sel.
(%)
-
(%)
(%)
100
100
100
68
69
Butyl butyrate
96.7
79.5
82.2
7
8
9
7
7
7
7
7
7
7
0
1
2
3
4
5
6
Methyl caprylate octanol
Methyl laurate laurinol
90.9
93.4
100
100
1
1
6
7
Reaction condition: 1.2 g ester, 22.8 g n-hexane, catalyst 0.3 g, T = 230
oC, P = 5.0 MPa, Stirring rate = 800 rpm.
10
11
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
In summary, the core-shell structured Cu@C-N
Cu@C-H catalysts were successfully synthesized by the
pyrolysis of Cu-BTC and applied in the liquid-phase
hydrogenation of butyl butyrate. Cu@C-N and Cu@C-H
2
and
77
78 12
2
7
8
8
8
8
8
8
8
9
0
1
2
3
4
5
6
13
14
15
16
2
2
catalysts maintained the octahedral structure of Cu-BTC
precursor and most Cu NPs were encapsulated into the carbon
shell. The interaction between copper species and oxygenated
groups on carbon surface prevented the migration and
aggregation of Cu species during the pyrolysis process. The
2
+
characterization results showed that Cu species was self-
87
0
reduced into Cu
because of the generation of some reduced gases, such as CO
and H . The comparison between the activity of Cu/AC-N
and Cu/AC-H
instead of CuO were the real active sites for the liquid-phase
hydrogenation of ester. Moreover, Cu@C-N catalyst showed
2
O and Cu during the pyrolysis process
88 17
89
9
0
18
2
2
0
91 19
2
catalysts indicated that Cu and Cu O species,
2
9
9
9
9
9
9
2
3
4
5
6
7
20
21
22
K. Zhao, Y. Liu, X. Quan, S. Chen and H. Yu, ACS Appl. Mater.
Interfaces 2017, 9, 5302.
Y. Wang, Y. Shen, Y. Zhao, J. Lv, S. Wang, X. Ma, ACS catal.
2015, 5, 6200.
T Miyake, T. Makino, S. Taniguchi, H. Watanuki, T. Niki, S.
shinizu, Y. Kojima, M. Sano, Appl. Catal. A-Gen, 2009, 364, 108.
P. Yuan, Z. Liu, W. Zhang, H. Sun, S. Liu, Chinese J. catal.,2010,
31, 769.
2
a higher activity due to the high Cu species dispersion, which
should be attributed to the inhibiting effect of the carbon shell
to the aggregation of copper species. Furthermore, Cu@C-H
2
catalyst prepared by the pyrolysis-reduction method
exhibited the highest catalytic activity, and the appropriate
98
99 23
+
0
Cu /Cu ratio should play a key role since a balance between 100
the activation of ester and H is crucial important for the ester
hydrogenation. Meanwhile, a high conversion and almost
100% selectivity have been obtained on Cu@C-H catalyst in
2
2
the hydrogenation of esters to corresponding alcohols,
demonstrating its extensive application in aliphatic alcohols
synthesis.
We are grateful to the financial support from the
National Nature Science Foundation of China (U1510203,