Facile Preparation of Oxygen-Vacancy-Mediated Mn₃O₄ for Catalytic Transfer Hydrogenation of Furfural

Abstract

The conversion of biobased furfural (FF) into furfuryl alcohol (FA) has immense industrial significance; however, the catalyst preparation methods for the conversion of FF to FA are demanding. We demonstrated a facile method, direct calcination of manganese(II) acetate tetrahydrate, to prepare an oxygen-vacant Mn 3 O 4 catalyst for the catalytic transfer hydrogenation (CTH) of FF to FA. The characterization results of oxygen-vacant Mn 3 O 4 along with commercial and conventional Mn 3 O 4 indicate that surface oxygen vacancies, strong acid−base properties, and a porous structure facilitate the high yield of FA (>99%) obtained from FF at 220 °C for 4 h in isopropanol. The oxygen vacancy-mediated Mn 3 O 4 could be reused five times without noticeable activity loss. Moreover, we confirmed that Mn 3 O 4 obtained from various manganese(II) salts by the direct calcination method also exhibited good performance for the CTH of FF to FA.

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

“…Yang et al fabricated an oxygen-vacant Mn 3 O 4 catalyst via direct calcination of manganese( ii ) acetate tetrahydrate. 94 Compared to commercial and conventional Mn 3 O 4 , the oxygen-vacant Mn 3 O 4 possessed surface oxygen vacancies and strong acid–base properties with a porous structure, and gave complete FF conversion and >99% FFA selectivity with a lower E a of 66.1 kJ mol −1 in isopropanol at 493 K for 4 hours. The oxygen-vacant Mn 3 O 4 catalyst can be reused five times without significant loss of catalytic activity, and can be recovered via calcination in air at 623 K for 2 hours.…”

Precursor- and waste-free synthesis of spark-ablated nanoparticles with enhanced photocatalytic activity and stability towards airborne organic pollutant degradation

“…This phenomenon suggested lattice expansion stemming from an augmented presence of oxygen vacancies caused by the calcination process. 43 Remarkably, this broadening was even more pronounced compared to the sol–gel prepared MnO 2 sample, indicating a more substantial lattice distortion attributable to a higher concentration of oxygen vacancies.…”

“…This journal is © The Royal Society of Chemistry 2024 could be associated with the Mn-O stretching vibration of Mn 2+ in tetrahedral coordination within the hausmannite Mn 3 O 4 phase. 42,43 In contrast, the sol-gel prepared MnO 2 sample unveiled a distinct Raman spectrum, featuring bands at 220 cm −1 , 279 cm −1 , 370 cm −1 , 510 cm −1 , 570 cm −1 , 635 cm −1 , 680 cm −1 , and 740 cm −1 . The pronounced vibration at the band above 500 cm −1 is attributed to the internal MnO 6 octahedral Mn-O stretch and O-Mn-O bend modes, where the complex Raman spectrum showing multiple peaks reflects a lower symmetry of the Mn-O octahedral environment of the ramsdellite matrix with pyrolusite intergrowths.…”

Poly(divinylbenzene-maleic acid) Hollow Nanospheres Coordinated with Zirconium: An Effective Catalyst for the Catalytic Transfer Hydrogenation of Furfural to Furfuryl Alcohol

“…As one of the most versatile bioderived platform chemicals, furfural can be utilized as an eco-friendly intermediate to produce fine chemicals for chemical and pharmaceutical industries. , Furfuryl alcohol is one of the most important chemicals derived from the hydrogenation of furfural . Furfuryl alcohol can be used for the production of resins, polyurethane foams, polyesters, and pharmaceuticals. − …”