Ruthenium-tungsten alloy nanoparticles accelerate the cascade hydrogenation-ring opening of furfurals to linear ketones

doi:10.1016/S1872-2067(25)64911-4

Abstract

Abstract:

The metal-acid bifunctional catalyzed conversion of furfurals to linear ketones is crucial but challenging for sustainable chemical synthesis owing to the tendency for over hydrogenation and overacid-catalyzed reaction pathways over traditional catalysts. Herein, ruthenium-tungsten (RuW) alloy nanoparticle-supported catalysts (such as, RuW/SiO₂, RuW/Al₂O₃, RuW/C) were prepared via incipient wetness impregnation followed by H₂ reduction, showing a cascade hydrogenation-ring opening transformation of furfural to 5-hydroxy-2-pentanone with an unprecedented yield of 86.2% at a mild temperature of 80 °C. Catalytic mechanism studies confirmed that hydrogen spillover from RuW alloy sites to WO_x sites generated H⁺-H^- pairs in situ, which functioned as atypical active sites for the furfural hydrogenation step and offered Brönsted acidic sites for the ring opening of furan alcohol, thereby facilitating the facile preparation of 5-hydroxy-2-pentanone. Furthermore, the catalyst exhibited broad applicability for synthesizing linear ketones from various furfurals (i.e., 5-methyl furfural and 5-hydroxymethyl furfural). This study demonstrated interesting bifunctional catalysis through harnessing hydrogen spillover to form transient H⁺-H^- pairs, enabling a challenging cascade reaction pathway toward an efficient linear ketone synthesis.

Key words: RuW-WO_x interface, Bifunctional catalysis, Furfurals, Linear ketones, Hydrogen spillover

Peng Huang, Zhijun Xie, Yong Guo, Jun Wang, Ji-Jun Zou, Qiang Deng. Ruthenium-tungsten alloy nanoparticles accelerate the cascade hydrogenation-ring opening of furfurals to linear ketones[J]. Chinese Journal of Catalysis, 2026, 82: 337-347.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64911-4

https://www.cjcatal.com/EN/Y2026/V82/I3/337

Figures/Tables 4

Fig. 1. (A) XRD patterns of RuW/SiO2 and Ru/SiO2. (B) TEM image of RuW/SiO2. Raman spectra (C), Ru 3p XPS spectra (D), W 4f XPS spectra (E), and EXAFS k2-weighted χ(k) analysis (F) of RuW/SiO2 and Ru/SiO2.

Fig. 2. (A) Reaction pathway of FFA reaction. Product distribution curve over time over Ru/SiO2 (B) and RuW/SiO2 (C). (D) Catalytic performance of FFA reaction over various catalysts. (E) Recycling performance of RuW/SiO2 in FFA reaction. Catalytic performance of 5-methyl furfural (F) and 5-hydroxymethyl furfural (G) over different catalysts. Reaction conditions: H2O (15 mL), temperature (80 °C), reactant (1 mmol), H2 (1.0 MPa), Ru/SiO2 (100 mg), RuW/SiO2 (100 mg); (D) time (12 h); (E) time (4 h); (F,G) time (12 h). The products were quantified by GC.

Fig. 3. (A) Catalytic performance of FFA reaction over various catalysts. (B) FFA hydrogenation kinetic experiments over Ru/SiO2 and RuW/SiO2 under different FFA concentrations and H2 pressure. (C) FFA hydrogenation rate over Ru/SiO2 and RuW/SiO2 under different atmospheres. In-situ DRIFT spectra (D) and W 4f and O 1s XPS analysis (E) in NAP-XPS of H2-activated RuW/SiO2. (F) PD hydrogenation rate over Ru/SiO2 and RuW/SiO2. Reaction conditions: H2O (15 mL), temperature (80 °C), reactant (1 mmol). (A) catalysts (100 mg), H2 (1.0 MPa), time (24 h); (B) catalysts (20 mg), H2 (1.0 MPa) time (0.5 h); (C) catalysts (20 mg), H2/D2 (1.0 MPa) time (0.5 h); (F) catalysts (20 mg), H2 (1.0 MPa), time (0.5 h). The products were quantified by GC.

Fig. 4. (A) FA ring opening rate over Ru/SiO2 and RuW/SiO2 under different atmospheres. NH3-TPD (B) and Py-FTIR (C) spectra of various catalysts. (D) In-situ DRIFT spectra of adsorbed FA on various catalysts. (E) The adsorption kinetics of FA over different catalysts. Adsorption conditions: H2O (150 mL), catalyst (100 mg), FA (0.05 mmol), temperature (30 °C). The FA concentrations were quantified by UV-Vis. (F) Catalytic performance of FFA reaction over physical mixture of Ru/SiO2 and different catalysts. Reaction conditions: H2O (15 mL), temperature (80 °C), reactant (1 mmol); (A) catalysts (100 mg), H2/N2 (1.0 MPa); (F) Ru/SiO2 (100 mg), HZSM-5 (11 mg), W/SiO2 (100 mg), time (24 h). The products were quantified by GC.

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