Accurate restricted transition-state shape selective hydrogenation of furfural over zeolite confined Cu catalyst

doi:10.1016/S1872-2067(25)64741-3

Abstract

Abstract:

Transition-state shape selectivity plays a crucial role in catalytic systems where reactants and products exhibit comparable molecular dimensions, as it restricts the accessible configuration space of reaction intermediates. Herein, we designed a Cu@MFI catalyst by encapsulating Cu active sites within the well-defined micropores of MFI zeolite through a pore confinement strategy. This architecture preserves the zeolite framework integrity while maintaining unhindered internal mass transport, thereby enabling precise spatial control over transition-state configurations. Employing furfural hydrogenation as a probe reaction, the metal-zeolite synergy in Cu@MFI endowed the catalyst with exceptional activity (100% furfural conversion) and quantitative selectivity (100% furfuryl alcohol) at 70 °C, sustained across a broad temperature window. Mechanistic studies reveal that the transition-state shape selectivity effectively prevented H₂O interaction with the furan ring, offering valuable insights for other reaction systems seeking to exploit shape selectivity for specific transformations.

Key words: Biomass, Cu@MFI catalyst, Transition-state shape selectivity, Furfural hydrogenation, Metal-zeolite synergy

Wanying Liang, Guangyue Xu, Yao Fu. Accurate restricted transition-state shape selective hydrogenation of furfural over zeolite confined Cu catalyst[J]. Chinese Journal of Catalysis, 2025, 74: 71-81.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64741-3

https://www.cjcatal.com/EN/Y2025/V74/I7/71

Figures/Tables 6

Scheme 1. The accurate hydrogenation of furfural to furfuryl alcohol on Cu@MFI.

Fig. 1. Catalyst characterization and catalytic performance of various catalysts for FA to FOL. (a) The design and synthesis of Cu@MFI. (b-f) TEM and mapping image of Cu@MFI. (g) XRD patterns. (h) FT-IR spectra. (i) 29Si MAS NMR spectra. (j) Various Cu catalysts at low temperature (50 °C). (k) Various Cu catalysts at high temperature (130 °C). Reaction conditions: 1 mmol FA, 100 mg catalyst, 10 mL H2O, 4 MPa H2, 5 h.

Fig. 2. Analysis of Cu components. (a) XPS spectra of Cu 2p. (b) LMM Auger spectra of Cu. (c) H2-TPD profiles. (d) UV-vis spectra.

Fig. 3. Structure and location of Cu species in MFI zeolite predicted by DFT. (a) The zeolite model contained intra-cage Cu and secondary framework Cu. (b-e) Experimental (brown) and fitted (green) curves of the magnitude and imaginary part of the Fourier transform of the Cu K-edge k3-weighted EXAFS spectra of oxygen-activated Cu@MFI samples.

Fig. 4. Reaction mechanism and structure-performance: (a) Reaction mechanism. (b) Optimized structures for the aqueous-phase hydrogenation-rearrangement of FA to CPO and calculated energy profiles for the potential comparative free energy of FA to CPO on Cu@MFI. Energy barriers are reported to two decimal places in the in the activation energy discussion section to emphasize quantitative differences in transition-state configurations.

Fig. 5. Texture properties and catalytic performance. (a) Pore size distribution of Cu@MFI and Cu/S-1. (b) Cu@MFI at various temperature. (c) Catalytic local state density. (d) Cu@MFI at maximum condition. (e) Catalytic performance comparison of Cu@MFI and Pt/Cu@MFI. Reaction conditions: 1 mmol FA, 100 mg catalyst, 10 mL H2O, 4 MPa H2, 130 °C, 5 h.

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