Promotion effect of Fe in the selective hydrogenation of furfural with bimetallic NiFe catalysts

doi:10.1016/S1872-2067(26)64959-5

Abstract

Abstract:

The selective hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) over Ni catalysts offers a sustainable route for biomass valorization. However, the conventional Ni catalysts suffer from poor selectivity in FAL hydrogenation. Herein, we report that the moderate Fe doping in Ni/TiO₂ significantly enhances selectivity without compromising catalytic activity for the selective hydrogenation of FAL to FOL. Notably, Ni/Fe-TiO₂ catalyst with Fe content ≥ 4.9 wt% maintained > 90% selectivity toward FOL at nearly 100% conversion, whereas Ni/TiO₂ achieved only 38% under the identical condition. Combined experimental and theoretical studies revealed that the enhanced catalytic performance of Ni/Fe-TiO₂ originates from the dilution of contiguous Ni sites by Fe, which suppresses the further hydrogenation of FOL. Moreover, Fe sites exhibited a stronger affinity for carbonyl groups compared to Ni(0), indicating complementary role where Ni(0) primarily facilitates H₂ dissociation, while Fe sites play a critical role in carbonyl activation. These findings underscore the superior synergistic effect of bimetallic systems in promoting selective functional group transformation.

Key words: Bimetallic catalysts, Synergistic effect, Selective hydrogenation, Carbonyl groups

Xin Liu, Yezhou Yang, Jingru Yang, Maodi Wang, Qihua Yang. Promotion effect of Fe in the selective hydrogenation of furfural with bimetallic NiFe catalysts[J]. Chinese Journal of Catalysis, 2026, 83: 411-418.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64959-5

https://www.cjcatal.com/EN/Y2026/V83/I4/411

Figures/Tables 5

Fig. 1. HAADF-STEM images, Ni NPs size distributions (inset) and EDS mapping of Ni/TiO2 (a), Ni/Fe6.9-TiO2 (b). H2-TPR profiles (c), XPS spectra of Ni 2p3/2 (d), and Fe 2p3/2 (e) of Ni/TiO2 and Ni/Fe-TiO2 catalysts.

Fig. 2. Conversion of furfural (a) and selectivity to furfuryl alcohol (b) as a function of reaction time over Ni/TiO2 and Ni/Fe-TiO2. (c) Apparent TOF of furfural hydrogenation: (I) Ni/TiO2; (II) Ni/Fe2.2-TiO2; (III) Ni/Fe4.9-TiO2; (IV) Ni/Fe6.9-TiO2; (V) Ni/Fe8.4-TiO2 (Data was from the kinetic curve after the induction period). Reaction conditions: 100 °C, 2 MPa H2, 0.2 mmol furfural, 20 mg catalysts, 2 mL isopropyl alcohol.

Fig. 3. The effect of furfural concentration (a) and H2 pressure (b) for furfural hydrogenation over Ni/TiO2 and Ni/Fe6.9-TiO2. (c) The apparent activation barriers of Ni/TiO2 and Ni/Fe6.9-TiO2 for furfural hydrogenation.

Fig. 4. The potential energy surface diagrams of carbonyl hydrogenation of furfural on Ni (111) (a) and NiFe (111) (b).

Fig. 5. (a) Recycling stability of Ni/Fe6.9-TiO2 in furfural hydrogenation. Reaction conditions: 100 °C, 2 MPa H2, 0.2 mmol furfural, 20 mg catalysts, 2 mL isopropyl alcohol, t = 4 h. The PXRD patterns (b), the XPS spectra of Ni 2p3/2 (c), and the XPS spectra of Fe 2p3/2 (d) of Ni/Fe6.9-TiO2 after 5 cycles.

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