TY - JOUR
T1 - Ionic Liquid/Polyoxometalate Hybrid Catalyst with Tunable Functionalities for Boosting the Selectively Oxidative Transformation of Biobased Carbohydrates
AU - Li, Kaixin
AU - Huang, Lizhen
AU - Zhang, Yao
AU - Zhu, Ziteng
AU - Zhao, Jun
AU - Xia, Guang Jie
AU - Min, Yonggang
N1 - This work was financially supported by the National Natural Science Foundation of China (No. 22008037), Natural Science Foundation of Guangdong Province of China (2023A1515011751), Science and Technology Planning Project of Guangzhou city (2023B03J1285), the National Key R&D Program of China (2020YFB040810) and NSFC (U20A20340). G.J.X. acknowledge the financially supported from NSFC (No. 22203041) and Guangdong Basic and Applied Basic Research Foundation (No. 2021A1515110406)
Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/11/8
Y1 - 2023/11/8
N2 - Biomass oxidation by synergic catalysis appears to be an efficient and sustainable approach for biomass valorization. Here we demonstrate the oxidation of glucose and its upstream biomass derivatives to glycolic acid (GA) under O2 in the presence of polyoxometalates (POM) hybridized with ionic liquids (ILs). Particularly, 61.0% selectivity of GA with 88.2% conversion and excellent carbon balance was obtained by [C2COOHMIM]4PMoV. The catalytic system was also applicable to the oxidation of raw lignocellulose. The IL-POM hybrids exhibited excellent recyclability. Time-dependent reaction, temperature-dependent NMR, and computational studies revealed that IL with carboxyl groups was supposed to suppress over-oxidation via stabilization of sugar intermediates, while the superiority of V1/IL-POM originated from the single-substituted V on the 4H site of POM. Thus, the adsorption of protonated glucose was more exothermic and kinetically favorable with the barrier of 0.41 eV. This strategy is expected to provide clues for efficient biomass conversion over multifunctional catalysts.
AB - Biomass oxidation by synergic catalysis appears to be an efficient and sustainable approach for biomass valorization. Here we demonstrate the oxidation of glucose and its upstream biomass derivatives to glycolic acid (GA) under O2 in the presence of polyoxometalates (POM) hybridized with ionic liquids (ILs). Particularly, 61.0% selectivity of GA with 88.2% conversion and excellent carbon balance was obtained by [C2COOHMIM]4PMoV. The catalytic system was also applicable to the oxidation of raw lignocellulose. The IL-POM hybrids exhibited excellent recyclability. Time-dependent reaction, temperature-dependent NMR, and computational studies revealed that IL with carboxyl groups was supposed to suppress over-oxidation via stabilization of sugar intermediates, while the superiority of V1/IL-POM originated from the single-substituted V on the 4H site of POM. Thus, the adsorption of protonated glucose was more exothermic and kinetically favorable with the barrier of 0.41 eV. This strategy is expected to provide clues for efficient biomass conversion over multifunctional catalysts.
UR - http://www.scopus.com/inward/record.url?scp=85177885148&partnerID=8YFLogxK
U2 - 10.1021/acs.iecr.3c02496
DO - 10.1021/acs.iecr.3c02496
M3 - Journal article
AN - SCOPUS:85177885148
SN - 0888-5885
VL - 62
SP - 18337
EP - 18349
JO - Industrial and Engineering Chemistry Research
JF - Industrial and Engineering Chemistry Research
IS - 44
ER -