Paper
Green Chemistry
into the sealed autoclave. Nitrogen was used for purging
air inside the reactor and maintaining a certain pressure
to prevent boiling. After the reaction with a stirring speed of
600 rpm, the autoclave was cooled automatically, and the
liquid solution was separated from the solid mixture by
centrifugation. The solid catalyst was collected and washed
with deionized water and ethanol several times, followed by
desiccation at 80 °C overnight.
Notes and references
1 (a) L. Petrus and M. A. Noordermeer, Green Chem., 2006, 8,
861; (b) J.-P. Lange, Biofuels, Bioprod. Biorefin., 2007, 1, 39;
(c) A. Corma, S. Iborra and A. Velty, Chem. Rev., 2007, 107,
2411; (d) P. Gallezot, ChemSusChem, 2008, 1, 734;
(e) C. H. Zhou, X. Xia, C. X. Lin, D. S. Tong and
J. Beltramini, Chem. Soc. Rev., 2011, 40, 5588; (f) J. J. Wang,
J. X. Xi and Y. Q. Wang, Green Chem., 2015, 17, 737;
(g) C. Chatterjee, F. Pong and A. Sen, Green Chem., 2015,
17, 40.
2 (a) J. Lewkowski, ARKIVOC, 2001, 17; (b) Y. Roman-Leshkov,
J. N. Chheda and J. A. Dumesic, Science, 2006, 312, 1933;
(c) J. N. Chheda, Y. Roman-Leshkov and J. A. Dumesic,
Green Chem., 2007, 9, 342; (d) R. Rinaldi and F. Schüth,
Energy Environ. Sci., 2009, 2, 610; (e) R. J. van Putten,
J. C. van der Waal, E. de Jong, C. B. Rasrendra, H. J. Heeres
and J. G. de Vries, Chem. Rev., 2013, 113, 1499;
(f) J. L. Song, H. L. Fan, J. Ma and B. X. Han, Green
Chem., 2013, 15, 2619; (g) R. Weingarten, A. Rodriguez-
Beuerman, F. Cao, J. S. Luterbacher, D. M. Alonso,
J. A. Dumesic and G. W. Huber, ChemCatChem, 2014, 6,
2229.
The collected liquid solution was filtered through 0.22 μm
pore-size filters prior to analysis. The main products in the
resultant solution were identified based on the standard com-
pounds and their structures were further confirmed by GC-MS
(Agilent 7890 GC with Agilent 5975C inert MSD) equipped with
an HP-INNO Wax column (30 × 0.25 mm, film thickness,
0.25 μm). These products in the reaction mixture were quanti-
fied by using HPLC apparatus (Shimadzu LC-20AD) equipped
with an Aminex HPX-87H Ion Exclusion Column (300 mm ×
7.8 mm) operating at 50 °C and a differential refraction detec-
tor (RID-10A) based on the external standard method. The
eluent used at a flow rate of 0.65 mL min−1 was a 12 mM
H2SO4 aqueous solution. The conversion of microalgae was
calculated based on the TOC data using the equation: Conver-
sion = (moles of carbon in the resultant liquid determined
by TOC) ÷ (moles of carbon in microalgae determined by using
a CHNS analyzer) × 100%. The yields of sugars, HMF, and LA
were calculated based on carbon via the equations: Yield =
(moles of carbon in the products determined by HPLC) ÷
(moles of carbon in the carbohydrate components of micro-
algae) × 100%, while the isolated yield of HMF was calculated
from the ratio of (moles of the generated HMF determined by
HPLC) to (moles of monosaccharides in microalgae). Besides,
there were also some polymer products, such as humins,
which were not quantified in this work due to the difficulty in
determination by HPLC.
3 (a) J. J. Wang, W. J. Xu, J. W. Ren, X. H. Liu, G. Z. Lu and
Y. Q. Wang, Green Chem., 2011, 13, 2678; (b) J. J. Wang,
J. W. Ren, X. H. Liu, G. Z. Lu and Y. Q. Wang, AIChE J.,
2013, 59, 2558; (c) Y. P. Xiao and Y. F. Song, Appl. Catal., A,
2014, 484, 74.
4 (a) M. Moliner, Y. Roman-Leshkov and M. E. Davis, Proc.
Natl. Acad. Sci. U. S. A., 2010, 107, 6164; (b) Y. Roman-
Leshkov, M. Moliner, J. A. Labinger and M. E. Davis, Angew.
Chem., Int. Ed., 2010, 49, 8954; (c) E. Nikolla, Y. Román-
Leshkov, M. Moliner and M. E. Davis, ACS Catal., 2011, 1,
408; (d) J. J. Wang, J. W. Ren, X. H. Liu, J. X. Xi, Q. N. Xia,
Y. H. Zu, G. Z. Lu and Y. Q. Wang, Green Chem., 2012, 14,
2506; (e) R. Bermejo-Deval, R. Gounder and M. E. Davis,
ACS Catal., 2012, 2, 2705; (f) S. Roy, K. Bakhmutsky,
E. Mahmoud, R. F. Lobo and R. J. Gorte, ACS Catal., 2013,
3, 573; (g) R. Bermejo-Deval, M. Orazov, R. Gounder,
S. J. Hwang and M. E. Davis, ACS Catal., 2014, 4, 2288;
(h) Y. P. Li, M. Head-Gordon and A. T. Bell, ACS Catal.,
2014, 4, 1537; (i) H. J. Cho, P. Dornath and W. Fan, ACS
Catal., 2014, 4, 2029.
Conclusions
In summary, we have presented a one-pot approach to produce
HMF in high yields from aquatic microalgae (Chlorococcum
sp.) under mild reaction conditions over the commercial
cheap H-ZSM-5 catalyst. To the best of our knowledge, this is
the first report on the production of HMF from aquatic
biomass. Production of HMF from microalgae should go
through the steps of degradation, hydrolysis, isomerization
and dehydration. Experimental results demonstrated that pro-
teins and lipids in microalgal cells benefitted the HMF stabi-
lity in water. Besides, ball-milling pretreatment or addition of
another organic solvent enhanced the productivity of HMF
from microalgae.
5 H. Jadhav, C. M. Pedersen, T. Solling and M. Bols, Chem-
SusChem, 2011, 4, 1049.
6 (a) Y. J. Pagán-Torres, T. Wang, J. M. R. Gallo, B. H. Shanks
and J. A. Dumesic, ACS Catal., 2012, 2, 930;
(b) D. M. Alonso, S. G. Wettstein, M. A. Mellmer,
E. I. Gurbuz and J. A. Dumesic, Energy Environ. Sci., 2013,
6, 76; (c) J. M. R. Gallo, D. M. Alonso, M. A. Mellmer and
J. A. Dumesic, Green Chem., 2013, 15, 85; (d) M. H. Tucker,
R. Alamillo, A. J. Crisci, G. M. Gonzalez, S. L. Scott and
J. A. Dumesic, ACS Sustainable Chem. Eng., 2013, 1,
554.
Acknowledgements
We acknowledge financial support provided by the National
Natural Science Foundation of China (21406255).
7 (a) S. Stucki, F. Vogel, C. Ludwig, A. G. Haiduc and
M. Brandenberger, Energy Environ. Sci., 2009, 2, 535;
Green Chem.
This journal is © The Royal Society of Chemistry 2015