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3 T. Ishida, H. Watanabe, T. Takei, A. Hamasaki, M. Tokunaga and M.
and the benzyl alcohol conversion rate (Fig. 5), but for the other
two kinds of species, N3 and N4, no correlation with the activity
results can be established (Fig. S3). It is suggested in literature
that a lone pair of electrons in pyridinic N1 endows the
materials a more active physicochemical property.17 Pyridinic
N1 has been reported to be the most active sites for ORR, sulfur
removal, and dehydrohalogenation due to the formation of
chemically active sites (pyridine-like defects), localized areas of
higher electron density in the catalytic reaction.18 Seen from the
aforementioned results, it seems that pyrrolic N2 also appears
to play a decisive role in the model reaction as well as pyridinic
N1. A little deviation may be caused by some undefined surface
defects and different graphitization degree of nanocarbons.
In order to study the general applicability of the mesoporous
nitrogen-doped nanocarbon materials, various benzylic
alcohols were tested as substrates. The desired nitriles were
obtained in >84 % yields when benzylic alcohols substituted
with electron-donating groups such as -Me, -OMe were
employed (Table 2, entries 1-7). Benzylic alcohols substituted
with various electron-withdrawing groups, such as −F, −Cl, −Br,
and –CF3 were selectively transformed (Table 2, entries 8-11). It
is worth noting that heterocycles thiophene-2-methanol could
also be used as substrates in the title reaction and afforded the
heterocyclic nitriles in up to 75 % yield (Table 2, entry 12).
Attempts were made to oxidize the challenging aliphatic
alcohols. Unfortunately, due to the inactive aliphatic alcohols,
no product was noted (Table 2, entry 13). To demonstrate the
synthetic potential of the meso-N/C-900 catalyst system, a
gram-scale experiment of aerobic oxidative cyanidation of
benzyl alcohol was carried out, and a yield of 78 % was achieved
for the desired product (Scheme S1).
DOI: 10.1039/C6CC09151B
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In conclusion, we produced nitrogen-doped nanocarbons
with a mesoporous structure and a surface area of 906 m2g-1.
When used as a metal-free carbocatalyst for ammoxidation of
alcohols to nitriles, the obtained meso-N/C-900 showed good
activity, selectivity and recyclability, owing to the accessible
mesopores and the effective pyridinic/pyrrolic-N doping. This
study represents a major breakthrough in the development of
ammoxidation of alcohols to nitriles.
We gratefully acknowledge the financial support from the
National Natural Science Foundation of China (21403219),
(21273225), and the National Engineering Laboratory for
Methanol to Olefins.
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4 | J. Name., 2012, 00, 1-3
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