A regulatable oxidative valorization of furfural with aliphatic alcohols catalyzed by functionalized metal-organic frameworks-supported Au nanoparticles

作者：Ning, Liangmin; Liao, Shengyun^*; Liu, Xuguang; Guo, Pengfei; Zhang, Zhenya; Zhang, Haigang; Tong, Xinli^*

来源：Journal of Catalysis, 2018, 364: 1-13.

DOI：10.1016/j.jcat.2018.04.030

• Metal-organic framework (MOFs)
• Au nanoparticles
• Oxidative condensation
• Furfural
• Biomass transformation

The oxidative upgrading of furfural (FUR) and aliphatic alcohols is an important way to produce desirable precursor of jet fuel or value-added furanic compound. Therein, developing a highly active catalytic system with switchable product selectivity still remains a challenge. In this work, we report a novel strategy on regulating the oxidative condensation and oxidative esterification of FUR with aliphatic alcohol in the presence of molecular oxygen. Firstly, Au@Ui0-66 is prepared using different methods and employed as the catalyst for the oxidative valorization of FUR with methanol. It is found that the impregnation reduction -H-2 (1-H) method is the best where a 100% selectivity of methyl-2-furoate with a complete conversion was obtained using Au@UiO-66 as catalyst. Then, a series of metal -organic frameworks (MOFs) supported Au nanoparticles (Au@UiO-66-X) such as Au@UiO-66, Au@UiO-66-NH2, Au@UiO-66-NO2, Au@UiO-66-COOH and Au@UiO-66-NH3Cl have been prepared with I-H method and employed for oxidative valorization of furfural with ethanol. Experimental results showed that, in "FUR-ethanol-O-2" system, the Au@UiO-66-X can efficiently regulate the oxidative condensation and oxidative esterification as two competitive reaction pathways. With Au@UiO-66-COOH as the catalyst, the oxidative condensation process is dominant in which 84.1% selectivity of furan-2-acrolein is attained; Meanwhile, the Au@UiO-66 is beneficial to the occurrence of oxidative esterification and generation of ethyl-2-furoate. At last, based on the catalyst characterization and the numerous control experiments, a possible catalytic reaction mechanism for conversion of FUR is proposed.

• 出版日期2018-8
• 单位天津理工大学