TY - JOUR
T1 - Mechanistic role of protonated polar additives in ethanol for selective transformation of biomass-related compounds
AU - Guo, Haixin
AU - Duereh, Alif
AU - Su, Yaqiong
AU - Hensen, Emiel J.M.
AU - Qi, Xinhua
AU - Smith, Richard Lee
N1 - Funding Information:
The authors are grateful to the financial support from JSPS Grant in Grant-in-Aid for Early-Career Scientists (No. 19K15347, Japan), the project program of Tohoku University for promotion of gender equality (Japan), the National Natural Science Foundation of China (NSFC, Nos. 21577073 and 21876091, China) and the Natural Science Fund for Distinguished Young Scholars of Tianjin (No. 17JCJQJC45500, China).
Funding Information:
The authors are grateful to the financial support from JSPS Grant in Grant-in-Aid for Early-Career Scientists (No. 19K15347 , Japan), the project program of Tohoku University for promotion of gender equality (Japan) , the National Natural Science Foundation of China (NSFC, Nos. 21577073 and 21876091 , China) and the Natural Science Fund for Distinguished Young Scholars of Tianjin (No. 17JCJQJC45500 , China). Appendix A
PY - 2020/5/5
Y1 - 2020/5/5
N2 - We report on a combined experimental, spectroscopic and theoretical study of acid catalysed dehydration-etherification of fructose in ethanol for understanding the mechanistic role of polar solvent additives and product selectivity. Herein, we show that polar solvent additives (e.g. tetrahydrofuran, acetone, acetonitrile, gamma-valerolactone, dimethyl sulfoxide) protonated with a common solid acid catalyst in ethanol allow transformation of biomass-related compounds into desired dehydration or etherification products. Fructose in ethanol with DMSO additive is selectively transformed into 5-hydroxymethylfurfural with negligible formation of 5-ethoxymethylfurfural due to preferential DMSO protonation according to its polarity. Spectroscopic methods and density functional theory show that additives having higher polarity than ethanol are readily protonated and act as the key catalytic protonation species and as the key stabilization species for reaction intermediates. Understanding the mechanism of protonated polar additives in reaction systems allows one to tailor selectivity in acid-catalyzed dehydration-etherification schemes and to develop sustainable chemistry for biomass resources.
AB - We report on a combined experimental, spectroscopic and theoretical study of acid catalysed dehydration-etherification of fructose in ethanol for understanding the mechanistic role of polar solvent additives and product selectivity. Herein, we show that polar solvent additives (e.g. tetrahydrofuran, acetone, acetonitrile, gamma-valerolactone, dimethyl sulfoxide) protonated with a common solid acid catalyst in ethanol allow transformation of biomass-related compounds into desired dehydration or etherification products. Fructose in ethanol with DMSO additive is selectively transformed into 5-hydroxymethylfurfural with negligible formation of 5-ethoxymethylfurfural due to preferential DMSO protonation according to its polarity. Spectroscopic methods and density functional theory show that additives having higher polarity than ethanol are readily protonated and act as the key catalytic protonation species and as the key stabilization species for reaction intermediates. Understanding the mechanism of protonated polar additives in reaction systems allows one to tailor selectivity in acid-catalyzed dehydration-etherification schemes and to develop sustainable chemistry for biomass resources.
KW - Acid-catalyzed protonation mechanism
KW - Product selectivity
KW - Proton transfer
KW - Stabilization
KW - Sustainable chemistry
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U2 - 10.1016/j.apcatb.2019.118509
DO - 10.1016/j.apcatb.2019.118509
M3 - Article
AN - SCOPUS:85075970227
VL - 264
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
SN - 0926-3373
M1 - 118509
ER -