ACS Catalysis
Letter
levulinate yielded 93% GVL, although a relatively higher
reaction temperature and prolonged duration are needed (entry
11). It is well-known that aldehydes are generally more reactive
than ketones due to the steric hindrance and electron-donating
nature of the alkyl group in ketone.
21666008), Department of Biotechnology (Government of
India), and Key Technologies R&D Program of China
(2014BAD23B01).
REFERENCES
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The study has also been extended to explore the intra-
molecular hydrogen transfer of C3−C6 aldoses to the
corresponding ketoses with ZrPN in water (Table S5). The
product distribution of glucose isomerization reaction was
found to be 52% glucose, 36% fructose, and 5% mannose at 90
°C for 50 min (Table S5, entry 1), which is comparable to that
of Sn-Beta zeolite-mediated catalytic systems.21 Only 6−10%
and 21% of fructose was formed when using ZrO2 and ZrPPh
as catalysts, respectively, inferring the positive role of Zr (Lewis
acid sites) in the framework of ZrPN combined with the
adjacent basic sites on accelerating fructose yield (Table S6).
The poisoning experiments proved the synergic effect of acid−
base sites in ZrPN on glucose-to-fructose isomerization (Table
S5, entries 2 and 3). These results clearly indicate that Lewis
acid sites present in ZrPN cannot be hampered by water,
thereby enhancing the catalytic activity. In constrast, Al-zeolites
cannot catalyze glucose isomerization due to weakening of
Lewis acid sites in water.22 The other aldoses including xylose,
erythrose, and glyceraldehyde can also give good yields of
corresponding ketoses with ZrPN (Table S5, entries 4−6).
Besides isomerization, epimerization also takes place in low
degree over ZrPN for C4−C6 sugars, and the in situ-formed C3
ketose dihydroxyacetone from glyceraldehyde tends to be
further converted to lactic acid via pyruvic aldehyde.23
In summary, we have demonstrated that the mesoporous
ZrPN nanohybrid with high surface area and enhancive Lewis
acid (zirconium) and base (alkylphosphate and amino groups)
centers can be synthesized by a facile and template-free
approach. The bifunctional nanohybrid exhibited remarkable
catalytic activity toward formation of near quantitative yields of
valuable alcohols from biomass-derived carboxides via direct
hydrogen transfer, and it was also effective for aldose-to-ketose
isomerization in water. The obtained results from these studies
clearly indicate that ZrPN can efficiently catalyze the inter- and
intramolecular hydrogen transfer reactions and can be
extrapolated to other similar lignocellulose-derived substrates
for upgrading biomass.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
Experimental details of catalyst preparation and charac-
terization; catalytic performance and mechanism (PDF)
AUTHOR INFORMATION
Corresponding Authors
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We are grateful to the reviewers for valuable suggestions. The
work is financially supported by the International S&T
Cooperation Program of China (2010DFB60840), National
Natural Science Foundation of China (21576059 and
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