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Table 2 Recycle of PZS-2.0 for catalytic conversion of fructose to
Notes and references
HMFa
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Run
Conversion/%
Selectivity/%
HMF yield/%
1
2
3
4
5
99.7
95.3
93.4
92.0
90.6
93.9
97.0
97.0
96.8
95.1
93.6
92.4
90.6
89.1
86.2
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´
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results.39 The O-triazine intermediate (A) was rstly formed on
the surface of PZS-NPs, followed by the protonation step to form
intermediate B, and then the formation of 2-hydroxymethyl-5-
hydroxylmethylene-tetrahydro-furan-3,4-diol. HMF was nally
generated aer the loss of the two water molecules. During the
process, the interactions between PZS-ZPs and fructose as well
as intermediate products should provide an enhancement in
each dehydration step.
Finally, reusability and recyclability of PZS-NPs were evalu-
ated as well on PZS-2.0, and the experimental results were
compiled in Table 2. As expected, the selectivity of HMF was well
kept aer 5 cycles, and the catalytic activity of PZS-2.0 was
decreased merely from 93.6% to 86.2%. However, the reduced
active P–Cl groups due to site covering or substituted Cl should
be responsible for the lost activity.
In summary, a heterogeneous catalyst of polyphosphazene
nanoparticles has been developed for highly efficient conversion
of fructose to HMF. Under relatively mild conditions, HMF was
produced with a 97.2% yield in 3 wt% fructose solution and
a 85.9% yield in 30 wt% fructose solution at 90 ꢀC for 0.5 h,
which is the rst example concerning polymeric nanoparticle
catalysts used for fructose conversion. Moreover, it has been
substantially veried that the as-prepared polyphosphazene
nanoparticle catalyst possesses the following outstanding
properties: (1) unique electron-withdrawing polymer backbone
activating the P–Cl catalytic sites for a much higher catalytic
activity; (2) high selectivity, recyclability and stability; (3) being
environmentally friendly without the utilizing strong proton acid
and any metal. Therefore, we believe this strategy with the
concept of structure-enhanced catalytic performance opens
a new pathway for developing highly active, green and degrad-
able heterogeneous catalysts, and efficient chemical technolo-
gies for dehydration of fructose to HMF and other biomass
conversion as well.
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Acknowledgements
We are grateful to Sino-UK higher education research partner-
ship sponsored by British council and Chinese scholarship
council. This work was supported by National Science Foun-
dation of China (Grant No. 21474017), National Science and
Technology Key Project of China (Grant No. 2012AA020204),
Shanghai Science and Technology Committee (Grant No.
14DZ2273900) and the China Postdoctoral Science Foundation
(Grant No. 2015M571487).
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