Microenvironment modulation around frustrated Lewis pairs in Ce-based metal-organic frameworks for efficient catalytic hydrogenation

doi:10.1016/S1872-2067(25)64695-X

Abstract

Abstract:

The development of solid frustrated Lewis pairs (FLPs) catalysts with porous structures is a promising strategy for advancing green hydrogenation technologies and has garnered significant attention. Leveraging the diverse oxidation states and structural tunability of cerium-based metal-organic frameworks (Ce-MOFs), this study employed a competitive coordination strategy utilizing a single carboxylate functional group ligand to construct a series of MOF-808-X (X = -NH₂, -OH, -Br, and -NO₂) featuring rich solid-state FLPs for hydrogenation of unsaturated olefins. The -X functional group serves as a microenvironment, enhancing hydrogenation activity by modulating the electronic properties and acid-base characteristics of the FLP sites. The unique redox properties of elemental cerium facilitate the exposure of unsaturated Ce sites (Ce-CUS, Lewis acid (LA)) and adjacent Ce-OH (Lewis base (LB)) sites within the MOFs, generating abundant solid-state FLP (Ce-CUS/Ce-OH) sites. Experimental results demonstrate that Ce-CUS and Ce-OH interact with the σ and σ* orbitals of H-H, and this "push-pull" synergy promotes heterolytic cleavage of the H-H bond. The lone pair electrons of the electron-donating functional group are transmitted through the molecular backbone to the LB site, thereby increasing its strength and reducing the activation energy required for H₂ heterolytic cleavage. Notably, at 100 °C and 2 MPa H₂, MOF-808-NH₂ achieves complete conversion of styrene and dicyclopentadiene, significantly outperforming MOF-808. Based on in-situ analysis and density functional theory calculations, a plausible reaction mechanism is proposed. This research enriches the theoretical framework for unsaturated olefin hydrogenation catalysts and contributes to the development of efficient catalytic systems.

Key words: Frustrated Lewis pairs, Microenvironment modulation, Defect, Ce-based metal-organic frameworks, Catalyst, Hydrogenation

Xu Xinmeng, Xi Zuoshuai, Gao Hongyi, Zhao Danfeng, Liu Zhiyuan, Ban Tao, Wang Jingjing, Zhao Shunzheng, Wang Ge. Microenvironment modulation around frustrated Lewis pairs in Ce-based metal-organic frameworks for efficient catalytic hydrogenation[J]. Chinese Journal of Catalysis, 2025, 75: 59-72.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64695-X

https://www.cjcatal.com/EN/Y2025/V75/I8/59

Figures/Tables 7

Scheme 1. Illustration of the synthesis process of MOF-808-X and its hydrogenation process.

Fig. 1. FT-IR (a) and XRD (b) characterization of MOF-808 series. TEM diagram of MOF-808 (c), MOF-808-NH2 (d), MOF-808-OH (e), MOF-808-Br (f) and MOF-808-NO2 (g). (h) STEM and EDX spectra of MOF-808-Br.

Fig. 2. N2 adsorption and desorption curves (a) and pore size distributions (b) of MOF-808 series. 1H NMR characterization (c) and UV-vis DRS spectra (d) of MOF-808 series materials.

Fig. 3. Ce 3d (a), O 1s (b) XPS, the ratio of Oad/Ototal and Ce3+/(Ce3++Ce4+) (c) of the MOF-808 series catalysts. Mean and standard deviation of three tests. XANES spectra (d,e), the extracted EXAFS signals (f), and FT-EXAFS spectra (g) of k3-weighted Ce L3-edge for MOF-808, MOF-808-NH2, Ce(NO3)3 and [(NH4)2][Ce (NO3)6]. k3-weighted Ce L3-edge WT-EXAFS contour plots of MOF-808 (h) and MOF-808-NH2 (i).

Fig. 4. Styrene (a,b) and DCPD (c,d) hydrogenation performance of MOF-808 series catalysts. (a,c) Different kinds of monocarboxylic functional ligands (A: MOF-808, B: MOF-808-NH2, C: MOF-808-OH, D: MOF-808-Br, E: MOF-808-NO2); (b,d) 4-aminobenzoic acid ratio.

Fig. 5. CO2-TPD (a), NH3-TPD (b), CDCl3-FTIR (c), and Py-FTIR (d) characterization of MOF-808 series catalysts. (e) Radar chart of the pore structure and chemical properties of MOF-808 series materials. (f) Influences of LA sites or LB sites of MOF-808-NH2 on the catalytic activity.

Fig. 6. (a) H2-TPD characterization of MOF-808 series catalysts. The differential in situ DRIFTS spectra for MOF-808-NH2 (b) and MOF-808-NO2 (c) in H2 (5%)/Ar(95%) atmosphere at 373 K. The Ce 3d XPS spectra of MOF-808-NH2 (d) and MOF-808-NO2 (e) before and after H2 activation. (f) FTIR spectra of DCPD adsorption on the surface of different samples. (g) Energy profile of H2 dissociation at FLP sites in MOF-808-NH2 and MOF-808-NO2. IGMH (h) and charge density difference plot (i) of MOF-808-NH2.

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