TY - JOUR
T1 - CaCl2molten salt hydrate-promoted conversion of carbohydrates to 5-hydroxymethylfurfural
T2 - an experimental and theoretical study
AU - Lin, Changqu
AU - Chai, Chaoqun
AU - Li, Yuanzhang
AU - Chen, Jiao
AU - Lu, Yanyu
AU - Wu, Hongli
AU - Zhao, Lili
AU - Cao, Fei
AU - Chen, Kequan
AU - Wei, Ping
AU - Ouyang, Pingkai
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2021.
PY - 2021/3/7
Y1 - 2021/3/7
N2 - Alkaline earth metal salts are environmentally friendly and economical. They have attracted much attention in the process of biomass conversion, especially for isomerization and dehydration. However, the lack of understanding of the alkaline earth metal-mediated catalytic mechanism prevents the achievement of high HMF yields from glucose or fructose. Herein, we performed experimental and theoretical studies on CaCl2-catalyzed glucose-to-fructose isomerization and fructose-to-HMF dehydration. In CaCl2solution, the highest fructose yield (33.6%) from glucose can be achieved at 80 °C. Meanwhile, the presence of CaCl2in fructose-to-HMF dehydration notably improved fructose conversion. A “one-pot” isomerization-dehydration of glucose to prepare HMF was designed and 100% conversion and 52.1% HMF yield were obtained. The CaCl2solution can be reused for five runs while maintaining catalytic activity without regeneration. Through1H NMR,13C NMR, DOSY-NMR and DFT calculations, we concluded that the coordination between the C1/C2 sites of the β-glucopyranose tautomer and CaCl2promoted the 1,2-intramolecular hydride shift of glucose, thus rapidly converting glucose into fructose. Similarly, Ca2+can complex with the C2/C6-OH of β-d-fructofuranose and stabilize this tautomer, which easily forms HMF. This is the main reason that CaCl2can promote the preparation of HMF from fructose.
AB - Alkaline earth metal salts are environmentally friendly and economical. They have attracted much attention in the process of biomass conversion, especially for isomerization and dehydration. However, the lack of understanding of the alkaline earth metal-mediated catalytic mechanism prevents the achievement of high HMF yields from glucose or fructose. Herein, we performed experimental and theoretical studies on CaCl2-catalyzed glucose-to-fructose isomerization and fructose-to-HMF dehydration. In CaCl2solution, the highest fructose yield (33.6%) from glucose can be achieved at 80 °C. Meanwhile, the presence of CaCl2in fructose-to-HMF dehydration notably improved fructose conversion. A “one-pot” isomerization-dehydration of glucose to prepare HMF was designed and 100% conversion and 52.1% HMF yield were obtained. The CaCl2solution can be reused for five runs while maintaining catalytic activity without regeneration. Through1H NMR,13C NMR, DOSY-NMR and DFT calculations, we concluded that the coordination between the C1/C2 sites of the β-glucopyranose tautomer and CaCl2promoted the 1,2-intramolecular hydride shift of glucose, thus rapidly converting glucose into fructose. Similarly, Ca2+can complex with the C2/C6-OH of β-d-fructofuranose and stabilize this tautomer, which easily forms HMF. This is the main reason that CaCl2can promote the preparation of HMF from fructose.
UR - http://www.scopus.com/inward/record.url?scp=85103008074&partnerID=8YFLogxK
U2 - 10.1039/d0gc04356g
DO - 10.1039/d0gc04356g
M3 - 文章
AN - SCOPUS:85103008074
SN - 1463-9262
VL - 23
SP - 2058
EP - 2068
JO - Green Chemistry
JF - Green Chemistry
IS - 5
ER -