Porous Zr–Thiophenedicarboxylate Hybrid for Catalytic Transfer Hydrogenation of Bio-Based Furfural to Furfuryl Alcohol

• Published in: Catalysis letters Vol. 149; no. 7; pp. 1845 - 1855
• Main Authors: Wang, Tao, Hu, Aiyun, Xu, Guangzhi, Liu, Chen, Wang, Haijun, Xia, Yongmei
• Format: Journal Article
• Language: English
• Published: New York Springer US 01.07.2019; Springer; Springer Nature B.V
• Subjects: Acetic acid; Adsorption; Alcohols; Carbonyl compounds; Carbonyls; Catalysis; Catalysts; Catalytic activity; Chemistry; Chemistry and Materials Science; Furfural; Furfuryl alcohol; Hydrogenation; Industrial Chemistry/Chemical Engineering; Organic acids; Organometallic Chemistry; Physical Chemistry; X ray photoelectron spectroscopy; Zirconium; Carbonyl compounds; Zr–thiophenedicarboxylate hybrid; Furfural; DUT-69(Zr); Furfuryl alcohol; Catalytic transfer hydrogenation
• ISSN: 1011-372X; 1572-879X
• DOI: 10.1007/s10562-019-02748-0

Furfural (FAL) is one of the most important biomass-derived platform compounds. The catalytic transformation of FAL was investigated with three porous Zr–thiophenedicarboxylate hybrids for the production of furfuryl alcohol (FOL). Three Zr-based catalysts, including DUT-67(Zr), DUT-68(Zr) and DUT-69(Zr) were synthesized through a facile assembly of 2,5-thiophenedicarboxylate acid with ZrCl 4 using the acetic acid as a modulator under hydrothermal conditions. These catalysts were also characterized using FT-IR, XRD, SEM, TEM, N 2 adsorption–desorption, XPS and TG. The specific surface area of the DUT-69(Zr) is smaller than that of the DUT-68(Zr) and slightly larger than that of the DUT-67(Zr), but it has a relatively large pore volume and pore diameter. Although all three catalysts showed excellent catalytic activity towards the catalytic transfer hydrogenation of FAL into FOL, the DUT-69(Zr) material has slightly higher catalytic activity than the other two catalysts. Besides, considering the cost of catalyst preparation, the DUT-69(Zr) material was used as the optimal catalyst and studied in detail. A high FOL yield of 92.2% at 95.9% FAL conversion was achieved at 120 °C for 4 h over DUT-69(Zr). Meanwhile, the DUT-69(Zr) could be reused more than six times with a minor decrease in catalytic activity. Finally, a plausible mechanism for catalytic transfer hydrogenation of carbonyl compounds to produce corresponding alcohols was presented based on the results of the experiments and previous reports. Graphical Abstract