Dual Metal–Acid Pd-Br Catalyst for Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural (HMF) to 2,5-Dimethylfuran at Ambient Temperature

Abstract

Supported metal catalysts have found broad applications in heterogeneous catalysis. In the conventional bifunctional catalyst, the active metal sites are associated with the metal nanoparticles, while the acid sites are usually localized over the oxide support. Herein, we report a novel type of supported metal bifunctional catalyst, which combined the advantages of the promotion and bifunctionality. The catalyst was designed by the pretreatment of supported palladium catalysts with bromobenzene. The promotion with bromine creates Brønsted acid sites, which are localized directly on the surface of metal nanoparticles. An intimacy between metal and acid functions in this bifunctional catalyst generates unique catalytic properties in hydrodeoxygenation of 5-hydroxymethylfurfural to dimethylfuran, occurring with the yield up to 96% at ambient temperature under 5 bar of H2. The catalyst exhibits stable catalytic performance.

Tunable HMF hydrogenation to furan diols in a flow reactor using Ru/C as catalyst

“…The depletion of fossil resources together with their contribution to environmental issues related to CO 2 emissions have stimulated research towards the synthesis of chemicals from renewable resources, such as lignocellulosic biomasses [1]. In this regard, 5-hydroxymethylfurfural (HMF) is a key platform-chemical, accessible from monosaccharides and polysaccharides [2][3][4][5][6][7][8][9], and the precursor for several value-added products, such as 2,5furandicarboxylic acid (FDCA), 2,5-dimethylfuran (DMF), 2,5-bis (hydroxymethyl)furan (BHMF), and 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) [9][10][11][12][13][14][15][16][17][18].The two last compounds are obtained from the hydrogenation of the aldehyde group (BHMF) and also of the furanic ring (BHMTHF), as reported in Scheme 1.…”

Role of the Bromide on the Hydrodebenzylation of 2,4,6,8,10,12‐Hexabenzyl‐2,4,6,8,10,12‐hexaazaisowurtzitane (HBIW)

“…The affinity between halide anion and the palladium increased in the following order: Cl<Br<I [32] . The medium interaction between bromide and palladium facilitated the absorption of HBIW and the desorption of the intermediate on the surface of the palladium [33] . More interestingly, HBr exhibited a better catalytic performance than KBr in terms of yield, and it seems that H + can also improve the catalytic performance in terms of yield.…”

“…[32] The medium interaction between bromide and palladium facilitated the absorption of HBIW and the desorption of the intermediate on the surface of the palladium. [33] More interestingly, HBr exhibited a better catalytic performance than KBr in terms of yield, and it seems that H + can also improve the catalytic performance in terms of yield. However, TADBIW was not obtained after adding acids (HClO 4 /H 2 SO 4 /CH 3 COOH), which can be attributed to the ring-opening after the isowurtzitane was protonated.…”

Continuous‐Flow Synthesis of 5‐Hydroxymethylfurfural, Furfural from Monosaccharides: A Simple, Fast, and Practical Method

“…[1][2][3][4][5] 2,5-Dimethylfuran has been regarded as a potential platform chemical, which is easily prepared by the hydrodeoxygenation of 5-hydroxymethylfurfural (HMF). [2,[6][7][8] As seen in Figure 1, HMF has been known as an essential raw material in the production of valuable compounds such as levulinic acid, [9][10][11] 2,5-furandicarboxaldehyde and 2,5-furandicarboxylic acid, [12][13] 1,5-bis(5-(hydroxymethyl)furan-2-yl)penta-1,4-dien-3-one [14] , which are known as key precursors for biofuel, polymers, and energy technology. However, high cost is the main obstacle hindering the commercialization of HMF ($1119.30/100 g, 99 % purity, Sigma-Aldrich).…”

“…The conversion of biomass into biofuels and value‐added chemicals plays a vital role in sustainable chemistry to address the depletion of fossil fuels [1–5] . 2,5‐Dimethylfuran has been regarded as a potential platform chemical, which is easily prepared by the hydrodeoxygenation of 5‐hydroxymethylfurfural (HMF) [2,6–8] . As seen in Figure 1, HMF has been known as an essential raw material in the production of valuable compounds such as levulinic acid, [9–11] 2,5‐furandicarboxaldehyde and 2,5‐furandicarboxylic acid, [12–13] 1,5‐bis(5‐(hydroxymethyl)furan‐2‐yl)penta‐1,4‐dien‐3‐one [14] , which are known as key precursors for biofuel, polymers, and energy technology.…”