Selective aerobic oxidation of the biomass-derived precursor 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under mild conditions over a magnetic palladium nanocatalyst

Abstract

A new method for the selective aerobic oxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) has been developed employing a magnetically separable [γ-Fe 2 O 3 @HAP-Pd(0)] catalyst. The catalyst was prepared by the exchange of Pd 2+ with Ca 2+ in γ-Fe 2 O 3 @HAP, followed by reduction of the Pd 2+ to Pd(0) nanoparticles, and well characterized by TEM, XRD and XPS. The catalyst showed high activity in the oxidation of HMF to FDCA in water, with 97% HMF conversion and a 92.9% yield of FDCA under optimal reaction conditions. The method developed has demonstrated some advantages, including its sole requirement of a stoichiometric base, and high catalytic performance under atmospheric oxygen, even in air. More importantly, the γ-Fe 2 O 3 @HAP-Pd(0) catalyst was readily separated from the reaction solution using an external magnetic field and was successfully reused during five consecutive reaction runs while retaining its catalytic effectiveness. This study provides a green and sustainable method for the production of valuable chemicals from renewable resources.

Selective oxidation of 5-hydroxymethyl furfural over non-precious metal heterogeneous catalysts

“…The literature survey for the oxidation of HMF to FDCA indicated that this reaction has been performed using stoichiometric amounts of oxidants and expensive catalytic systems containing noble metals such as Pt [17][18][19][20][21][22], Pd [23][24][25][26], Au [27][28][29][30][31][32], Ru [33], or their alloys [34][35][36][37][38][39][40][41]. In addition, the presence of a base is crucial in order to facilitate the desorption of the resulted acid from the catalytic surface.…”

Aerobic oxidation of 5-hydroxymethylfurfural (HMF) effectively catalyzed by a Ce0.8Bi0.2O2−δ supported Pt catalyst at room temperature

“…It is also a promising chemical intermediate for the preparation of ne chemicals, pharmaceuticals and other materials. [13][14][15][16] Though various catalysts have been applied successfully in HMF oxidation to FDCA, long reaction time, high temperature and high molar ratio of the precious metal to HMF were oen demanded to obtain a high FDCA yield. 2 The oxidation of HMF to FDCA comprises an alcohol oxidation and an aldehyde oxidation (Scheme 1).…”

Conversion of Furans by Baeyer-Villiger Monooxygenases

“…The oxidation of HMF or other furans to FDCA has been achieved mainly by metal-based catalysis [4][5][6][7]. Yet, the search for an efficient chemical process for converting HMF into valuable building blocks such as FDCA is still ongoing.…”