Angewandte Chemie International Edition
10.1002/anie.201803977
COMMUNICATION
and NBU400 may not serve as the efficient hydrogenation catalysts. material might be able to activate other small molecules like CO ,
2
Although the B2 structure shows a higher Lewis acidity than B1,
CO, NO and SO as the FLP did.
2
NBU400 with organic surface most likely disfavor the hydrogen
[
22]
transfer. On the other hand, NBU600 has the Lewis pairs with a
localized 흿 electron network as shown in Figure 5, which is
capable of fulfilling the hydrogenation process. Remarkably,
Keywords: Hydrogenation • Lewis pair • Heterogeneous
catalysis • Nanocarbon • Metal free catalysis
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1]
2]
3]
4]
5]
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NBU600 can efficiently catalyze the reaction even at 100 C, with
0.4% conversion and 98% selectivity within 6 hours (entry 6).
Furthermore, at 160 C, this conversion can reach up to 97.4% with
selectivity of 99%. In contrast to UDD1000 and NBU400,
NBU600 shows no selectivity decrease even at 220 C as shown in
entry 8. This, therefore, demonstrates a good prospect of the doped
Lewis pair in the graphitic structure for the hydrogenation reaction.
A series of other C=C bond-containing substrates were also tested,
and carbon catalyst has exhibited high reactivities. In addition,
NBU600 can also efficiently catalyze the nitrobenzene reduction
with hydrogen (Table S3). Detail time conversion plot, recycling
experiments and characterization of the used NBU600 are also
conducted and given in SI (Figure 14-19).
3
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Table 1. Cyclooctene hydrogenation with different samples.
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T
t
/h
Conv.
/%
Sel.
/%
Yield
/%
Cat.
o
/
C
none
160
160
220
160
220
100
160
220
12
12
12
12
12
6
10.3
9.8
66
96
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92
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98
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UDD1000
UDD1000
NBU400
NBU400
NBU600
NBU600
NBU600
9.3
18.4
6.4
11.2
5.9
7
800-7805.
[
[
[
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99.1
6.7
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29.9
96.4
98.8
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Experimental conditions: 10 mg catalyst, 200 µL
cyclooctene, 100 µL C H as internal standard, 100 bar H2,
stirring speed: 500 rpm.
[
[
1
0
22
4
80, 175-183.
In summary, the Lewis acidity and basicity of the in-situ doped B
and N on the graphitic carbon surface are demonstrated by NMR.
[
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The DFT calculations predict that the facile H activation on these
2
[
[
Lewis pairs follows a heterolytic cleavage mechanism. The
2
obtained Lewis pairs in the sp -hybridized structure of NBU600
1
30, 12632-12633.
can efficiently activate H in the solvent free reactions with various
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2
C=C bond-containing substrates. This finding provides a new
hydrogenation method in heterogeneous catalysis, and provides a
promising direction for the application of carbon materials. For
example, with controllable regulation of the doped surface, carbon
6
13.
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