Reduced Cu–Co–Al Mixed Metal Oxides for the Ring-Opening of Furfuryl Alcohol to Produce Renewable Diols

Abstract

The ring-opening of furfuryl alcohol to diol products, including 1,2-pentanediol and 1,5-pentanediol, is investigated over reduced Cu–Co–Al mixed metal oxides in a liquid phase batch reactor under H2 pressure. These catalysts are synthesized through the calcination of layered double hydroxides (LDH) to yield well-dispersed, porous mixed metal oxides, which upon reduction displayed activity toward diols, mainly the valuable monomer 1,5-pentanediol. The addition of Cu facilitated the reduction of Co oxide species at lower temperatures, and under optimized conditions, a yield toward 1,5-pentanediol of 44% (total diol yield of 62%) was achieved. Various characterization techniques including temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS) are employed to elucidate the structure of the catalysts, suggesting the formation of both metallic (Co and Cu) and oxide (CoO) species after reduction and passivation. Ultimately, this study demonstrates the promising characteristics that nonprecious multimetal catalysts have for the conversion of biomass derived platform molecules to plastic precursors.

Single-step catalytic conversion of furfural to 2-pentanol over bimetallic Co–Cu catalysts

“…For example, Cu-Co-Al mixed metal oxides that were reduced at 400°C were examined for FOL (which is the initial and common intermediate in all pathways considered here, see Scheme 1) conversion at 140°C, where it was seen that ∼62% yields of pentanediols formation occured. 38 In that study, it was argued that CoO x was critical for this process. In another study, Co-Cu/Al 2 O 3 catalysts were reduced at 280°C prior to FF HDO and it was proposed that existing of Cu-CoO x species facilitated 78% selectivity to MF at 220°C when using 2-propanol as a solvent.…”

Hydrogenation of furfural by noble metal-free nickel modified tungsten carbide catalysts

“…5,11 While furfural has moved in to the limelight of research on biomass derived resource streams, only little research has been done on its ring opening to produce pentanediol and the majority of said research focuses on the production of 1,5-PeD. 12 Most of the catalysts studied for the production of 1,2-PeD are based on noble metals like Ru, 6 Rh, [13][14][15][16][17][18] Pd 19,20 and Pt. 3,4,[21][22][23] Most notable are two platinum-based catalysts.…”

Hydro(deoxygenation) Reaction Network of Lignocellulosic Oxygenates

“…The RO of FOL to diol products, including 1,5‐PeD, over the reduced form of mixed‐metal oxides, in which both metallic (Co and Cu) and oxide (CoO) species are involved, a hydrogenated metal surface is supported by the metal oxides . Similarly, 2‐furancarboxylic acid (FCA) can be deoxygenated to result in valeric acid on titania‐supported Pt−MoO x /TiO 2 by using varied loading amounts of Pt and Mo .…”