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Green Chemistry
Page 6 of 8
ARTICLE
Journal Name
In the 3st run, the degree of delignification still remained 90%, and
the total lignin monomers yield was determined as 30 wt% with
good selectivity to 4-propanolphenols 3 (Table S8).
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8
and B. F. Sels, Energy Environ. Sci., 201D7O, 1I:010, .11053591/-C185G5C70.3511C
W. Schutyser, T. Renders, S. Van den Bosch, S. F. Koelewijn,
G. T. Beckham and B. F. Sels, Chem. Soc. Rev., 2018, 47, 852-
908.
Z. Sun, B. Fridrich, A. de Santi, S. Elangovan and K. Barta,
Chem. Rev., 2018, 118, 614-678.
In the context of
a sustainable and economically viable
biorefinery, the survivability of (hemi)cellulose components in the
solid pulp is important, as they can be valorized via downstream
processing. We measured the compositions of solid pulp after the
after the removal of catalyst (Table S9). Under 220 oC and 12 h
conditions, the retentions of cellulose and hemicellulose were
determined as 90% and 78%, respectively. In the case of high
9
10 L. Cao, I. K. M. Yu, Y. Liu, X. Ruan, D. C. W. Tsang, A. J. Hunt,
Y. S. Ok, H. Song and S. Zhang, Bioresour Technol, 2018, 269,
465-475.
11 Biorefineries–Industrial Processes and Products, ed. B. Kamm,
P. R. Gruber and M. Kamm, Wiley-VCH, Weinheim, 2006.
12 Aqueous Pretreatment of Plant Biomass for Biological and
Chemical Conversion to Fuels and Chemicals, ed. C. E.
Wyman, John Wiley & Sons, Chichester, 2013.
13 S. Constant, H. L. J. Wienk, A. E. Frissen, P. D. Peinder, R.
Boelens, D. S. Van Es, R. J. H. Grisel, B. M. Weckhuysen, W. J.
J. Huijgen, R. J. A. Gosselink and P. C. A. Bruijnincx, Green
Chem., 2016, 18, 2651–2665.
o
temperature (260 C and 8 h), high preservation of cellulose (90%)
was obtained, with observation of slight decrease of hemicellulose
retention (67%). Obviously, hemicellulose easily undergoes
degradation under high-temperature conditions.
14 S. Van den Bosch, W. Schutyser, R. Vanholme, T. Driessen, S.
F. Koelewijn, T. Renders, B. De Meester, W. J. J. Huijgen, W.
Dehaen, C. M. Courtin, B. Lagrain, W. Boerjan and B. F. Sels,
Energy Environ. Sci., 2015, 8, 1748-1763.
15 S. Van den Bosch, W. Schutyser, S. F. Koelewijn, T. Renders,
C. M. Courtin and B. F. Sels, Chem. Commun., 2015, 51,
13158-13161.
16 T. Renders, E. Cooreman, S. Van den Bosch, W. Schutyser, S.
F. Koelewijn, T. Vangeel, A. Deneyer, G. Van den Bossche, C.
M. Courtin and B. F. Sels, Green Chem., 2018, 20, 4607-4619.
17 M. V. Galkin and J. S. M. Samec, ChemSusChem, 2014, 7,
2154-2158.
18 X. Huang, J. Zhu, T. I. Korányi, M. D. Boot and E. J. M. Hensen,
ChemSusChem, 2016, 9, 3262-3267.
19 T. Parsell, S. Yohe, J. Degenstein, T. Jarrell, I. Klein, E. Gencer,
B. Hewetson, M. Hurt, J. I. Kim, H. Choudhari, B. Saha, R.
Meilan, N. Mosier, F. Ribeiro, W. N. Delgass, C. Chapple, H. I.
Kenttämaa, R. Agrawal and M. M. Abu-Omar, Green Chem.,
2015, 17, 1492-1499.
20 T. Renders, W. Schutyser, S. Van den Bosch, S. F. Koelewijn,
T. Vangeel, C. M. Courtin and B. F. Sels, ACS Catal., 2016, 6,
2055-2066.
Conclusions
In summary, chemodivergent reductive catalytic fractionation
of eucalyptus sawdust is demonstrated by using Ni@ZIF-8
catalyst in MeOH. High phenolic monomer yields close to the
theoretical maximum were obtained, next to high retentions
of cellulose and hemicellulose components. The
chemoselectivity of hydrogenolysis of lignin can be tuned by
the choice of reaction temperature and time, thus affording 4-
propanol- and 4-propyl-substituted phenols as major product,
respectively. The reactivity study of β-O-4 mimics and
corresponding monomeric phenols provided important
information for understanding the mechanistic details.
Conflicts of interest
There are no conflicts to declare.
21 I. Kumaniaev, E. Subbotina, J. Savmarker, M. Larhed, M. V.
Galkin and J. Samec, Green Chem., 2017, 19, 5767-5771.
22 X. Huang, X. Ouyang, B. Hendriks, O. Morales, J. Zhu, T. I.
Koranyi, M. Boot and E. J. M. Hensen, Faraday Discuss., 2017,
202, 141-156.
23 Q. Song, F. Wang, J. Cai, Y. Wang, J. Zhang, W. Yu and J. Xu,
Energy Environ. Sci., 2013, 6, 994-1007.
Acknowledgements
We are grateful to National Natural Science Foundation of
China (No. 21776020), Fundamental Research Funds for the
Central Universities (No. 2018BLRD12) and National Key R&D
Program of China (2017YFB0307903) for support of this
research.
24 I. Klein, B. Saha and M. M. Abu-Omar, Catal. Sci. Technol.,
2015, 5, 3242-3245.
25 E. M. Anderson, M. L. Stone, R. Katahira, M. Reed, G. T.
Beckham and Y. Román-Leshkov, Joule, 2017, 1, 613-622.
26 S. Van den Bosch, T. Renders, S. Kennis, S. F. Koelewijn, G.
Van den Bossche, T. Vangeel, A. Deneyer, D. Depuydt, C. M.
Courtin, J. M. Thevelein, W. Schutyser and B. F. Sels, Green
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27 Y. Zhai, C. Li, G. Xu, Y. Ma, X. Liu and Y. Zhang, Green Chem.,
2017, 19, 1895-1903.
28 H. Luo, I. M. Klein, Y. Jiang, H. Zhu, B. Liu, H. I. Kenttämaa and
M. M. Abu-Omar, ACS Sustainable Chem. Eng., 2016, 4,
2316-2322.
29 E. M. Anderson, R. Katahira, M. Reed, M. G. Resch, E. M.
Karp, G. T. Beckham and Y. Román-Leshkov, ACS Sustainable
Chem. Eng., 2016, 4, 6940-6950.
30 J. Chen, F. Lu, X. Si, X. Nie, J. Chen, R. Lu and J. Xu,
ChemSusChem, 2016, 9, 3353-3360.
31 S. Wang, W. Gao, L.-P. Xiao, J. Shi, R.-C. Sun and G. Song, Sus.
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