Porous Zirconium Hydroxyphosphonoacetate: Catalyst for Conversion of Furfural into Furfuryl Alcohol

Abstract

Catalytic transfer hydrogenation (CTH) of the C=O bond has been considered to be one of the most important processes for the synthesis of fuels and chemicals. In this study, zirconium hydroxyphosphonoacetate (Zr‐HPAA) was synthesized by solvent‐thermal method for the transfer hydrogenation of furfural (FF) to furfuryl alcohol. As expected, the Zr‐HPAA, which comprises P−O‐Zr and C−O‐Zr linkages, shows high activity for catalytic transfer hydrogenation of FF to FA. Besides, the effects of time, temperature, catalyst dosage and solvent on the reaction were investigated in detail, with FF conversion (98%) and FA yield (96%) at 150 °C in 1.5 h. The activation energy (Ea) of the reaction was calculated as 47.04 kJ/mol and the lower activation energy was associated to the high catalytic activity of Zr‐HPAA. It is easy to separate catalyst after the reaction and the catalyst exhibits high activity for at least five reaction cycles.

Recent advances in the catalytic transfer hydrogenation of furfural to furfuryl alcohol over heterogeneous catalysts

“…Liu et al prepared zirconium hydroxyphosphonoacetate (Zr-HPAA) with P–O–Zr and C–O–Zr linkages via a solvent-thermal method for the CTH of FF to FFA. 104 98% FF conversion and 96% FFA yield were achieved with an E a of 47.04 kJ mol −1 in isopropanol at 423 K for 1.5 hours. The good stability of Zr-HPAA was demonstrated for at least five cycles without significant loss of activity.…”

Zirconium Phosphate Catalyzed Transformations of Biomass-Derived Furfural to Renewable Chemicals

“…Authors have shown that the adsorption of both butyl levulinate and 2-propanol over Lewis acid Zr sites in the MPV reduction step facilitates the formation of intermediate butyl 4-hydroxypentanoate, which is finally converted into γ-valerolactone (GVL) in the presence of the Brönsted acidity . Chen Liuand et al have also suggested the role of Lewis acid/base sites for the conversion of FAL to FOL over Zr–hydroxyphosphonoacetate . Thus, based on the acidity measurements, FAL adsorption, and literature reports, the reaction mechanism is proposed in Scheme .…”

“…53 Chen Liuand et al have also suggested the role of Lewis acid/ base sites for the conversion of FAL to FOL over Zr− hydroxyphosphonoacetate. 56 Thus, based on the acidity measurements, FAL adsorption, and literature reports, the reaction mechanism is proposed in Scheme 2. In the first step, adsorption of 2-propanol occurs on Lewis acid Zr 4+ sites through oxygen; however, −H of the hydroxyl group in 2propanol binds with the Lewis base O 2− sites.…”

Recyclable Zr/Hf-Containing Acid-Base Bifunctional Catalysts for Hydrogen Transfer Upgrading of Biofuranics: A Review

“…The organometallic coordination polymerization catalyst has high catalytic activity and good molecular tailoring (Wang et al, 2016b;Liu et al, 2021e). By adjusting the microstructure of catalysts, such as the substituents of the ligand, the coordination atom, and the electronic and three-dimensional environment of the coordination center, the molecular design and assembly of the polymer can be realized at the molecular level (Erickson et al, 2015;Hu et al, 2018;Liu et al, 2019;Peng et al, 2021). In this way, the physical properties of polymers can be controlled, and various polymers with novel functions and stereoisomers can be obtained (Asghari and Yoshida, 2006;Dutta et al, 2012;Jain et al, 2015;Zhou et al, 2019a).…”

“…It is still necessary to further process the biomass feedstock to upgrade its functional groups (Dabros et al, 2018;Li et al, 2019b;Iglesias et al, 2020Tan et al, 2021. In the field of biomass upgrading, the most widely used approach is to convert biomass (e.g., cellulose and hemicellulose) into a series of furan compounds via cascade reactions (Scheme 1) (Zhou and Zhang, 2016;Liu et al, 2019;Chen et al, 2021b). Among furan compounds, c-valerolactone (GVL) is recognized as a kind of versatile chemical building block (Liu et al, 2021a;Kerkel et al, 2021;Delgado et al, 2022).…”