High Performance and Sustainable Copper-Modified Hydroxyapatite Catalysts for Catalytic Transfer Hydrogenation of Furfural

Abstract

Designing and developing non-noble metal-based heterogeneous catalysts have a substantial importance in biomass conversion. Meerwein-Ponndorf-Verley (MPV) reaction is a significant pathway for eco-friendly catalytic transfer hydrogenation (CTH) of biomass derived furfural into furfuryl alcohol. In this work, a series of copper-supported hydroxyapatite (HAp) catalysts with different copper loadings (2–20 wt.%) were prepared by a facile impregnation method and tested in the reduction of furfural to furfuryl alcohol using 2-propanol as a hydrogen donor. The structural and chemical properties of the synthesised catalysts were analysed by using various techniques (XRD, N2 sorption, SEM, TEM, UV-DRS, ICP, FTIR, TPR, TPD-CO2 and N2O titration). The effect of copper loading was found to be significant on the total performance of the catalysts. The results demonstrate that 5CuHAp catalyst possess highly dispersed copper particles and high basicity compared to all other catalysts. Overall, 5CuHAp exhibited highest conversion (96%) and selectivity (100%) at 140 °C at 4 h time on stream. The optimised reaction conditions were also determined to gain the high activity.

Recent advances in the catalytic transfer hydrogenation of furfural to furfuryl alcohol over heterogeneous catalysts

“…63 Putrakumar et al fabricated Cu-hydroxyapatite (HAp) catalysts via a facile impregnation method for the CTH of bio-derived FF. 64 5CuHAp (5 wt% Cu loading) exhibited the best catalytic performance because of its large active Cu surface area (210 m 2 g −1 ), highly dispersed copper particles, and higher basicity, giving >99% FFA selectivity at 96% FF conversion using isopropanol as the hydrogen donor at 413 K and 2 MPa N 2 for 4 hours. Weng et al fabricated silicalite-1 confined ultrasmall CuO catalysts (CuO@silicalite-1) for the CTH of FF to FFA.…”

Biomass-derived 2-methyltetrahydrofuran platform: a focus on precious and non-precious metal-based catalysts for the biorefinery

“…Calcium phosphate-based materials have been identified as useful catalysts or support materials for biomass catalytic conversion of fuels. [305][306][307][308][309] Pure hydroxyapatite (HAP) (Ca 10 (PO 4 ) 6 (OH) 2 ) has a combination of Brønsted acidic sites through P-OH interaction and Lewis acidic sites by virtue of its Ca 2+ ions, whereas basicity occurs via attached OH − and O 2− ions. 310,311 Since support to active metal phase interaction has shown to be vital for most MTHF synthesis routes, Ca 2+ of HAP can interact with active metals through cat-ionic exchange to promote such reactions.…”

Mechanism of Catalytic Transfer Hydrogenation for Furfural Using Single Ni Atom Catalysts Anchored to Nitrogen-Doped Graphene Sheets

“…Therefore, the MPV reduction has attracted increasing attention because of its green and safe hydrogenation reaction process. Many different types of catalysts including transition metals, − metal oxides, − zeolites, − and metal–organic frameworks ,− have been reported to be active for the CTH reactions.…”