Chelating-agent-free incorporation of isolated Ni single-atoms within BEA zeolite for enhanced biomass hydrogenation

doi:10.1016/S1872-2067(24)60272-X

Abstract

Abstract:

Precisely tailoring metal single-atoms within zeolite scattfolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis. Herein, we have successfully fabricated Ni single-atoms within BEA zeolite (Ni₁@Beta) through a facile in situ two-step hydrothermal strategy, notably without using any chelating agent for stabilizing Ni species. With the aid of advanced characterization techniques, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, etc., and combined with density functional theory calculations, the nature and micro-environment of isolated Ni species, which are incorporated within 6-membered rings and stabilized by four skeletal oxygens of Beta zeolite, have been identified. The as-obtained Ni₁@Beta exhibits a superior performance in terms of activity (with a turnover frequency value up to 114.1 h^-1) and stability (for 5 consecutive runs) in the selective hydrogenation of furfural, surpassing those of Ni nanoparticle analogues and previously reported Ni-based heterogeneous catalysts. This study provides an efficient strategy for the fabrication of non-noble metal single-atoms within zeolites, which could be of great help for the design of metal-zeolite combinations in the chemoselective reactions involved in biomass conversion and beyond.

Key words: : Nickel, Single-atoms, Zeolites, Catalytic hydrogenation, Biomass conversion

Meng Liu, Caixia Miao, Yumeng Fo, Wenxuan Wang, Yao Ning, Shengqi Chu, Weiyu Song, Ying Zhang, Jian Liu, Zhijie Wu, Wenhao Luo. Chelating-agent-free incorporation of isolated Ni single-atoms within BEA zeolite for enhanced biomass hydrogenation[J]. Chinese Journal of Catalysis, 2025, 71: 308-318.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60272-X

https://www.cjcatal.com/EN/Y2025/V71/I4/308

Figures/Tables 5

Scheme 1. Schematic illustration of the in situ two-step hydrothermal approach for the incorporation of Ni single-atoms within Beta zeolite.

Fig. 1. Electron microscopy analyses of the Ni1@Beta. (a) Low magnification STEM image. (b,c) High magnification STEM images. (d) Elemental mappings for Si, Al and Ni. AC-HAADF-STEM image (e) and its magnified AC-HAADF-STEM images (f) of selected regions. Isolated Ni atoms are marked in white circles.

Fig. 2. Structure of Ni1@Beta. Ni K-edge XANES spectra (a) and FT magnitude of the k2-weighted EXAFS in R space (b) for Ni1@Beta and Ni/Beta catalysts with comparison to a Ni foil and a NiO reference. (c) 6-MR motifs found in BEA zeolite. (d) Different configurations of Al sites in A1 ring. (e) The distances between the Ni atom and the first coordinated O atoms. (f) Electron charge density difference plot of Ni1@Beta with the most stable structure. Yellow and green colors indicate the accumulation and depletion of electron density, respectively.

Fig. 3. Catalytic performance and recyclability of Ni1@Beta and Ni/Beta. (a) Typical reaction networks for furfural hydrogenation. (b) Catalytic hydrogenation of furfural with different catalysts. a Reaction conditions: 0.3 g FF, 23.56 g isopropanol, 0.3 g catalyst, 10 bar H2, 110 °C, 1 h, 1000 r min-1. b Reaction conditions: 0.3 g FF, 23.56 g isopropanol, 0.3 g catalyst, 10 bar H2, 110 °C, 2 h, 1000 r min-1. (c) Literature survey of Ni-based heterogeneous catalysts for furfural hydrogenation [21,22,40????-45]. (d) Recyclability of Ni1@Beta in the selective hydrogenation of furfural. Reaction conditions: 0.3 g FF, 23.56 g isopropanol, 0.1 g catalyst, 10 bar H2, 110 °C, 1 h, 1000 r min-1. (e) Recyclability of Ni/Beta in the selective hydrogenation of furfural. Reaction conditions: 0.3 g FF, 23.56 g isopropanol, 0.4 g catalyst, 10 bar H2, 110 °C, 1 h, 1000 r min-1.

Fig. 4. Characterization of Ni1@Beta and Ni/Beta. H2-TPR profiles (a) and Ni 2p XPS spectra (b) of Ni/Beta and Ni1@Beta. FT-IR spectra of CO adsorbed at low temperature (-170 °C) on Ni1@Beta (c) and Ni/Beta (d).

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