Vapor Phase Hydrogenolysis of Furanics Utilizing Reduced Cobalt Mixed Metal Oxide Catalysts

Abstract

Vapor phase hydrogenolysis of both furfuryl alcohol and furfural are investigated over reduced Co based mixed metal oxides derived from the calcination of a layered double hydroxide precursor. Although a reduced cobalt‐aluminum oxide sample displays promising selectivity towards 2‐methylfuran (2‐MF) production, the addition of an Fe dopant into the oxide matrix significantly enhances the activity and selectivity per gram of catalyst. Approximately 82 % 2‐MF yield is achieved at high conversion if furfuryl alcohol is fed into the reactor at 180 °C over the reduced 3Co‐0.25Fe‐0.75Al catalyst. Based on structural characterization studies including temperature‐programmed reduction (TPR), X‐ray photoelectron spectroscopy (XPS), and in situ X‐ray absorption spectroscopy (XAS) it is suggested that Fe facilitates the reduction of Co, allowing for formation of more metallic species. Overall, this study demonstrates that non‐precious metal catalysts offer promise for the selective conversion of a key biomass oxygenate to a proposed fuel additive.

Kinetics of Furfural Hydrogenation over Bimetallic Overlayer Catalysts and the Effect of Oxygen Vacancy Concentration on Product Selectivity

“…Pure copper showed high selectivity toward furfuryl alcohol . Pure cobalt favored furfuryl alcohol, but 2‐methylfuran selectivity was also prominent at 200 °C and elevated pressures . Pure Pd showed high selectivity toward furan and tetrahydrofurfuryl alcohol, while furfuryl alcohol became a minor product .…”

“…[43] Pure cobalt favored furfuryl alcohol, but 2methylfuran selectivity was also prominent at 200°C and elevated pressures. [44][45][46] Pure Pd showed high selectivity toward furan and tetrahydrofurfuryl alcohol, while furfuryl alcohol became a minor product. [11] Bimetallic overlayer catalyst Co@Pd and Cu@Pd showed higher furfuryl alcohol selectivity.…”

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

“…Consequently, in this study, nonprecious MMO catalyts were investigated for the liquid phase ring-opening of FAL to increase ring-opening yields and create a better understanding of the nature of the structural domains in these complex materials. In our prior work, MMO materials have been shown to be a promising catalyst for the selective conversion of FUR/FAL alcohol to other products, specifically 2-methylfuran (2-MF) or THFA, excluding diol formation. , Reduction of the MMO catalysts was crucial in creating the bifunctionalities (metallic and oxide domains), and after different reduction procedures, we sought to determine the electronic environment of these compositionally complex catalysts. In this work, along with reactivity studies, X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) experiments were conducted to determine how the catalysts behaved under various reduction conditions.…”

Catalytic applications of layered double hydroxides in biomass valorisation

“…Comparison of 5 wt% Ru doped CoFe-and NiFe-LDH for 2,5-DMF production from HMF revealed CoFe-LDH favours 2,5-DMF production (98.2% yield in batch at 10 bar H2) 44. In this instance, Ru promoted 2,5-DMF production under harsher conditions than for undoped Co3Fe0.25Al0.75 systems,43 possibly reflecting a suboptimal 2:1 Co:Fe ratio in the support.…”

“…Hydrogenation, hydrogenolysis and hydrodeoxygenationand a more desirable 1 bar H2 pressure. Fe substitution into the Co lattice was proposed to increase 2-MF production, however high Fe contents resulted in metallic Fe phases and deactivation 43. Comparison of 5 wt% Ru doped CoFe-and NiFe-LDH for 2,5-DMF production from HMF revealed CoFe-LDH favours 2,5-DMF production (98.2% yield in batch at 10 bar H2) 44.…”