26
J. Zhang et al. / Catalysis Communications 35 (2013) 23–26
0
Cu0 and little unreduced NiO was found in the reduced samples.
The C2 catalyst prepared without calcination showed higher activity
for glucose hydrogenation when compared to that of calcined sample.
The acidic or alkaline medium did not favor sorbitol production. The
desired yield and selectivity of sorbitol on C2 catalyst were 73.2 and
93.4 % at reaction temperature and time of 398 K and 3 h with cata-
lyst dosage of 20 %.
in C3–C4 samples could not be easily reduced into Ni based on the re-
sults of XPS analysis. The highest level of 69.2 and 86.5% in the yield and
selectivity of sorbitol was achieved using non-calcined C2 catalyst.
In the following work, the C2 catalyst was modified with various
metallic elements such as Mg, Zn, Co, Cr and Fe, with the aim of en-
hancing hydrogenation reactivity. It can be seen from Table 2
(
non-calcined C5–C9 samples) that the Mg and Fe modified C2 cata-
lysts exhibited great glucose conversion, while the corresponding se-
lectivities towards sorbitol were lower. Note that the Zn modified C2
catalyst showed poor activity compared to other modified catalysts.
Through the comparison and analysis, the hydrogenation activity of
those added metals was not greater when compared to active Ni
and Cu catalysts, which were hardly applied in hydrogenation reac-
tions. On the other hand, it was inferred that these metals did not ap-
parently promote the activation of the C_O in glucose molecules,
thus leading to the decrease in the yield and selectivity of sorbitol.
Subsequently, the influence of reduction temperature on the activity
of C2 catalyst was studied. As seen in Table S1, the catalyst activity was
greatly improved by increasing reduction temperature from 623 to
Acknowledgments
This work was supported by the National High Technology Research
and Development Program of China (863 Program 2012AA101806),
the National Natural Science Foundation of China (No. 31270635),
and the International Cooperation Projects of Guangdong Province,
China (No. 2011B050400015).
Appendix A. Supplementary data
2
+
to Cu0
8
73 K. For Cu element, it could be easily reduced from Cu
2
+
in the precursors, because the reduction of Cu
was completed at
6
23 K under hydrogen atmosphere according to XPS analysis. However,
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the formation of hydrotalcite structure. The XRD and XPS tests of re-
duced catalysts indicated that the Cu
2
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was completely reduced to
Table 3
Effect of reaction mediums on the hydrogenation of glucose.
Medium
15 mmol/L H
52.1
SO
2 4
Deionized water 15 mmol/L NaOH
Sorbitol yield, %
Glucose conversion, % 66.3
Sorbitol selectivity, % 78.6
73.2
78.4
93.4
42.2
84.9
49.7
Reaction conditions: 2.0 g glucose, 0.4 g non-calcined C2 catalyst (reduction tempera-
ture: 873 K), 40 mL reaction medium, 398 K, 600 rpm, 3 h and 3 MPa H
2
.