Selective Hydrogenation of 5‐Hydroxymethylfurfural to 1‐Hydroxy‐2,5‐hexanedione by Biochar‐Supported Ru Catalysts

Abstract

The development of sustainable and efficient catalysts -namely Ru supported on activated biochars-is carried out for the selective hydrogenation of 5-hydroxymethylfurfural (HMF) to 1hydroxy-2,5-hexanedione (HHD). Activated biochars obtained from pyrolysis and steam-based physical activation of two different biomasses from animal (leather tannery waste; A Lw ) and vegetal (hazelnut shells; A HSw ) origins show completely different chemical, textural, and morphological properties. Compared to A Lw , after impregnation with 0.5 wt % Ru, A HSw , with inner micro-mesochannels and cavities and higher layer stacking disorder, leads to better trapping and anchoring of Ru nanoparticles on the catalyst and a suitable Ru single crystal dispersion. This leads to a highly active Ru/A HSw catalyst in the proposed reaction, giving more than 80 % selectivity to HHD and full HMF conversion at 100 °C with 30 bar H 2 for 3 h. Ru/ A HSw also shows promising performance compared to a commercial Ru/C catalyst.

Linear diketones as next-generation biomass-derived platform molecules: from heterogeneous catalytic synthesis to supply of high-end chemicals

“…The work from Rosseinsky et al 47 also confirms the direct correlation between hydrogenation activity (with 96% HMF conversion) and smaller Pd nanoparticle size ( d M = 3.5 ± 1.5 nm) through comparative experiments based on three Pd-based catalysts with different metal particle sizes, as shown in entries 1, 6 and 7 in Table 3. Similar results were also found by the works of Yang et al , 73 and Signoretto et al 85…”

“…The work from Rosseinsky et al 47 also confirms the direct correlation between hydrogenation activity (with 96% HMF conversion) and smaller Pd nanoparticle size (d M = 3.5 ± 1.5 nm) through comparative experiments based on three Pd-based catalysts with different metal particle sizes, as shown in entries 1, 6 and 7 in Table 3. Similar results were also found by the works of Yang et al, 73 and Signoretto et al 85 Rational modulation of metal sites has been proved to improve the catalytic activity and selectivity of HMF conversion to HHD. It had been demonstrated by Cao et al that bimetallic synergy could influence the catalytic performance of HMF conversion.…”

“…Interestingly, Brønsted acids have also been reported to promote the conversion of C 6 furan compounds to linear diketones together with Lewis acids. Ru/ A HSw ( A HSw , a biochar derived from hazelnut shells) was confirmed by Signoretto et al 85 to exhibit a better HMF conversion rate and HHD selectivity relative to the commercial Ru/C, as shown in entries 13 and 14 in Table 3. Its catalytic advantages were mainly attributed to the synergy between the Brønsted acid from the biochar support and the Lewis acid from the oxidized Ru species.…”

Carbonized Leather Waste: A Review and Conductivity Outlook

“…Carbonized leather wastes prove to be an efficient photocatalyst in the removal of phenol from water due to the presence of chromium(III) oxide [ 15 ], despite their small specific surface area and low porosity. Ruthenium supported on carbonized leather has been used as a catalyst for the selective hydrogenation of 5-hydroxymethylfurfural [ 100 ].…”

Hydrogen-mediated acid-base transformation of Ni supported Mo5N6 for hydrogenative rearrangement of furfural derivatives

“…Furfurals (furfural, 5-methyl furfural, and 5-hydroxymethyl furfural), important biomassderived platform chemicals, are produced from carbohydrates (xylose, L-rhamnose, and hexose). 1,2 The presence of abundant oxygen-containing bonds (i.e., C-O-C, C-OH, and C]O) and unsaturated groups (C]O and C]C) in furfurals aids in its conversion via cascade hydrogenation-acid/base catalysis such as hydrogenative ring opening to linear diketones/diols (e.g., 1,4-pentanediol, 2,5-hexanedione, and 2,5-hexanediol), [3][4][5][6] hydrogenative rearrangement to cyclopentanones (e.g., cyclopentanone and 3-methyl cyclopentanone) in water, [7][8][9] hydrogenative etherication to furan ethers (i.e., 2-alkoxymethyl furan and 2,5-bisalkoxymethyl furan), 10,11 and hydrogenative hydrogenolysis to methyl furans (i.e., 2-methyl furan and 2,5dimethyl furan) in alcohol. 12,13 Among these, cyclopentanones have garnered attention owing to their crucial role as a building block intermediate in the production of fragrances, pharmaceuticals, and fungicides.…”