One-pot Selective Conversion of Biomass-derived Furfural into Cyclopentanone/Cyclopentanol over TiO2 Supported Bimetallic Ni-M (M = Co, Fe) Catalysts

Abstract

One-pot selective conversion of biomass-derived furfural (FFald) into cyclopentanone (CPO) or cyclopentanol (CPL) using bimetallic nickel-based supported on TiO2 (denoted as Ni-M(3.0)/TiO2; M = Co and Fe; 3.0 is Ni/M molar ratio) have been investigated. Catalysts were synthesized via a hydrothermal method at 150 °C for 24 h, followed by H2 reduction at 450 °C for 1.5 h. X-ray Diffraction (XRD) analysis showed that the formation of Ni-Co alloy phase at 2θ = 44.2° for Ni-Co(3.0)/TiO2 and Ni-Fe alloy at 2θ = 44.1° for Ni-Fe(3.0)/TiO2. The amount of acid sites was measured by using ammonia-temperature programmed desorption (NH3-TPD). Ni-Co(3.0)/TiO2 has three NH3 desorption peaks at 180 °C, 353 °C, and 569 °C with acid site amounts of 1.30 µmol.g-1, 1.0 µmol.g-1, and 2.0 µmol.g-1, respectively. On the other hand, Ni-Fe(3.0)/TiO2 consisted of NH3 desorption peaks at 214 °C and 626 °C with acid site amounts of 3.3 µmol.g-1and 2.0 µmol.g-1, respectively. Both Ni-Co(3.0)/TiO2 and Ni-Fe(3.0)/TiO2 catalysts were found to be active for the selective hydrogenation of FFald to furfuryl alcohol (FFalc) at low temperature of 110 °C, H2 3.0 MPa, 3 h with FFalc selectivity of 81.1% and 82.9%, respectively. High yields of CPO (27.2%) and CPL (41.0%) were achieved upon Ni-Fe(3.0)/TiO2 when the reaction temperature was increased to 170 °C, 3.0 MPa of H2, and a reaction time of 6 h. The yield of CPO+CPL on the reused catalyst decreased slightly after the second reaction run, but the activity was maintained for at least three consecutive runs. Copyright © 2020 BCREC Group. All rights reserved

The Promotion Effect of Cu on the Pd/C Catalyst in the Chemoselective Hydrogenation of Unsaturated Carbonyl Compounds

“…Additionally, a notable high yield of cyclopentanone (CPO) and cyclopentanol (CPOL) was obtained when 1,4-dioxane or 1,4-dioxane-H2O mixture solvent was used. These results are very consistent with the previous work of Dewi Astuti et al [27] using bimetallic Ni-Fe(3.0)/TiO2 catalysts under the identical reaction conditions. Therefore, further investigation on the hydrogenolysis of FFald using bimetallic Pd-based catalysts will be reported in our upcoming manuscript.…”

“…It is well-known that furfural (FFald), a versatile and biogenic biomass-derived compound, which can be obtained from acidic dehydration of arabinose or xylose of hemicellulosic biomasses [24]. Further catalytic conversion of FFald via chemoselective hydrogenation, hydrogenolysis, hydrogenation-arrangement using both monometallic and bimetallic transition metal catalysts produced a variety of high value chemicals such as furfuryl alcohol (FFalc), tetrahydrofurfuryl alcohol (THFalc), methyl-furan (MeF), methyl tetrahydrofuran (MeTHF), pentanediol (PeD), and cyclopentanone (CPO) or cyclopentanol (CPOL) as shown in Scheme 1 [25][26][27].…”

Catalytic Transformation of Biomass-Derived Furfurals to Cyclopentanones and Their Derivatives: A Review

“…Nickel–cobalt and nickel–iron bimetallic catalysts supported on titanium dioxide were prepared, characterized, and applied for the hydrogenation of FF. 74 The catalysts were prepared by the hydrothermal method at 150 °C, followed by reduction with molecular hydrogen. The molar ratio of Ni/M (M = Co, Fe) was fixed to 3.0, and the catalysts were denoted as Ni–M(3.0)/TiO 2 .…”

“…Up to a 41% yield of CPL was obtained by using the Ni–Fe(3.0)/TiO 2 catalyst for 6 h at 170 °C under 3.0 MPa of H 2 pressure. 74 …”

“…As discussed in previous Section (Table , entry 34), Astuti et al synthesized the nickel-based heterogeneous bimetallic catalysts for the hydrogenation of FF in the aqueous medium. Up to a 41% yield of CPL was obtained by using the Ni–Fe(3.0)/TiO 2 catalyst for 6 h at 170 °C under 3.0 MPa of H 2 pressure …”