Silicalite-1 encapsulated Cu nanoclusters with La modification for enhanced performance in hydrogenation of furfural to furfuryl alcohol

doi:10.1016/S1872-2067(26)65125-X

Abstract

Abstract:

Selective hydrogenation of furfural (FFL) to furfuryl alcohol (FAL) represents a pivotal paradigm in sustainable biomass valorization. In this work, nanoscale Cu clusters were encapsulated in silicalite-1 (S-1) zeolite using in-situ synthesis, and further modified by a rare-earth element of La for regulating the catalyst microenvironment. The obtained La-Cu@S-1 can provide an enhanced performance in the FFL-to-FAL transformations, with 98.6% conversion of FFL and 99% selectivity of FAL at 110 °C, 20 bar H₂, and 3 h. Besides, La-Cu@S-1 shows a good stability without apparent catalyst deactivation upon four consecutive runs. Extensive characterization research reveals that La addition could provide anchoring sites for Cu nanoclusters via an enhanced electronic interaction, thereby effectively suppressing metal leaching and agglomeration during the liquid-phase catalysis. Additionally, La addition could modulate the zeolite microenvironment of encapsulated Cu nanoparticles and notably stabilize the conventionally unstable Cu⁺ species at a high proportion, even in a reductive H₂ atmosphere during catalysis, accounting for the enhanced activity and stability. This study showcases La modification as an efficient approach to rationally develop metal-zeolite combinations with enhanced performance, promoting potential utilization and development of rare-earth elements in the valorization of biomass and other renewable energy.

Key words: Zeolites, Encapsulation, Furfural, Hydrogenation, Rare-earth element

Han Xiang, Lu Lin, Yu Li, Qisong Yi, Chaoran Jiang, Rui Chen, Yuanshuai Liu, Na Sai, Jinlu He, Fenghua Bai, Wenhao Luo. Silicalite-1 encapsulated Cu nanoclusters with La modification for enhanced performance in hydrogenation of furfural to furfuryl alcohol[J]. Chinese Journal of Catalysis, 2026, 88: 382-392.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65125-X

https://www.cjcatal.com/EN/Y2026/V88/I9/382

Figures/Tables 8

Scheme 1. Schematic of the in-situ encapsulation approach for the preparation of the Cu@S-1 and La-Cu@S-1.

Table 1 The physicochemical properties of S-1 and different Cu-containing zeolites.

Catalyst	Loading ^a (wt%)		D_Cu ^b (%)	S_BET ^c (m²/g)	S_micro ^c (m²/g)	V_micro ^c (cm³/g)
Catalyst	La	Cu	D_Cu ^b (%)	S_BET ^c (m²/g)	S_micro ^c (m²/g)	V_micro ^c (cm³/g)
S-1	—	—	—	495	356	0.18
Cu@S-1	—	2.1	27.3	425	314	0.16
La-Cu@S-1	0.2	1.9	30.5	428	269	0.14
Cu@S-1 (Spent) ^d	—	1.9	26.6	404	227	0.12
La-Cu@S-1 (Spent) ^d	0.2	1.8	30.5	417	205	0.11

Fig. 1. STEM image (a) and HAADF-STEM images (b,c) of Cu@S-1 (Inset: Particle size distribution of Cu). STEM image (d) and HAADF-STEM images (e,f) of La-Cu@S-1 (Inset: Particle size distribution of Cu). EDX elemental mapping spectra of Cu@S-1 (g) and La-Cu@S-1 (h).

Fig. 2. (a) Reaction pathway for the hydrogenation of FFL. Time profiles of FFL conversion and products yield over Cu@S-1 (b) and La-Cu@S-1 (c). (d) Activity and selectivity comparison of different catalysts. Reaction conditions: 0.3 g furfural, 23.56 g isopropanol, 0.3 g catalyst, 20 bar H2, 110 °C, 1000 rpm, and 3 h. Recycling experiments of Cu@S-1 (e) and La-Cu@S-1 (f). Reaction conditions: 0.3 g furfural, 23.56 g isopropanol, 0.3 g catalyst, 20 bar H2, 110 °C, 1000 rpm, and 1 h. (g) Comparison with as-reported Cu-zeolite catalysts for the hydrogenation of FFL to FAL. The TOF was defined as moles of FAL per mol of surface Cu per hour.

Fig. 3. STEM image (a) and HAADF-STEM images (b,c) of Cu@S-1 (spent) (Inset: Particle size distributions of Cu). STEM image (d) and HAADF-STEM images (e,f) of La-Cu@S-1 (spent) (Inset: Particle size distributions of Cu). EDX elemental mapping spectra of Cu@S-1 (spent) (g) and La-Cu@S-1 (spent) (h).

Fig. 4. Cu 2p3/2 XPS spectra (a) and Cu LMM XAES spectra (b) of Cu@S-1, La-Cu@S-1, Cu@S-1 (spent), and La-Cu@S-1 (spent). (c) Proportions of different Cu species in Cu@S-1, La-Cu@S-1, Cu@S-1 (Spent), and La-Cu@S-1 (Spent). (d) H2-TPR profiles of Cu@S-1 and La-Cu@S-1.

Fig. 5. FT-IR-CO spectra of Cu@S-1 (a) and La-Cu@S-1 (b). Charge density difference of Cu@S-1 (c) and La-Cu@S-1 (d). The blue, green, orange, and red spheres denote Cu, La, Si, and O atoms, respectively; The yellow and cyan regions indicate electron accumulation and depletion, respectively.

Scheme 2. Schematic of the La effect on the catalytic performance of La-Cu@S-1 in the hydrogenation of FFL to FAL.

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