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Green Chemistry
DOI: 10.1039/C6GC02630C
ARTICLE
Journal Name
conversion of HMF was above 99% and the yield of DMF was
0.1%. THF was the best solvent among the solvent checked
Conclusions
9
CuCo®/NGr/α-Al
2
O
3
is very active and selective for the
with above 99% conversion and above 99% yield of DMF.
However, the conversion of HMF and the yield of DMF were
very low in nonpolar solvent cyclohexane (Table 4, entry 6).
conversion of HMF to DMF, and yield of DMF can be as high as
9% at optimized condition. The main reason for the very high
9
yield is that the catalyst is active for C–O bond cleavage and
C=O bond hydrogenation, but is not active for hydrogenation
of C=C bond in furan ring, and thus the by-products DHTHF and
DMTHF are not produced. The Cu and Co bimetal and pyrrolic-
N synergistically promoted the activity of the catalyst. This
work provides an effective route for the conversion of HMF to
2
H O was also not a good solvent for this reaction maybe
because the solubility of the reactant and product (Table 4,
entry 7).
Table 4. The effect of different solvents on the hydrogenalysis of HMF
Entry
reaction
Yields (%)
5-MF BHMF others
Conv. DMF over non-noble metal catalyst.
a
solvents
DMSO
DMF
49.8
67.6
66.7
90.1
>99
4.9
5-MFA
5.4
(%)
1
2
3
4
5
6
7
7.9
4.2
5..6
1.9
0
7.2
7.8
9.1
2.7
0
8.8
10.3
11.9
3.2
0
79.1
Acknowledgements
2-propanol
1-butanol
1,4-dioxane
THF
2.5
92.4
3.3
96.6
The authors thank the Recruitment Program of Global Youth
1.3
>99
Experts of China, the National Natural Science Foundation of
0
>99
China (21273253, 21373230) and Chinese Academy of Sciences
cyclohexane
1.5
1.7
1.3
2.8
1.6
2.7
0.4
13.5
(
KJCX2.YW.H30) for financial supports.
H
2
O
1.1
12.3
16.7
o
Reaction conditions: HMF (1 mmol), catalyst (100 mg), T (180 C), PH2 (2 MPa), t
a
(
16 h), stirring speed (600 rpm). others indicated unidentified products.
Notes and references
1
2
3
4
5
6
7
8
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Catalyst recyclability
0
The reusability of CuCo®/NGr/α-Al O catalyst was tested
2
3
for the hydrogenolysis of HMF to DMF. After the reaction, the
reaction mixture was centrifuged and the solid CuCo®/NGr/α-
Al O catalyst was recovered, followed by rinsing with THF and
2
013, 3(1), 41-46.
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2
3
2 3
centrifugation (5×20 mL). The CuCo®/NGr/α-Al O catalyst was
1
o
reused directly for the next run after drying at 80 C for 6 h in a
vacuum oven. The results in Figure 6 clearly showed that the
catalytic performance decreased after being reused for five
times. By XPS characterization (Figure S6), the content of
pyrrolic-N decreased from 73.7% to 60.5% after being reused
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1
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HMF Conversion
8
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2
0
0
0
0
0
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1
1
1
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1
2
3
4
5
Runs
Figure 6. Recyclability experiments with CuCo®/NGr/α-Al
2
O
3
catalyst in the
hydrogenolysis of HMF to DMF. Reaction conditions: HMF (1 mmol, 126 mg); catalyst 19 H. C. Zhou, J. L. Song, H. L. Fan, B. B. Zhang, Y. Y. Yang, J. Y.
(
100 mg); reaction temperature (180°C); solvent (THF, 2mL); reaction time (16 h);
Hu, Q. G. Zhu, B. X. Han, Green Chem., 2014, 16, 3870-3875.
stirring speed (600 rpm)
6
| J. Name., 2012, 00, 1-3
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