Achieving selective C−O bond cleavage of esters over monolayer NiMoS catalysts derived from oil-soluble polyoxometalates

doi:10.1016/S1872-2067(26)65104-2

Abstract

Abstract:

Sulfided NiMo catalysts can effectively hydrogenate oxygen-rich bio-oils into high quality hydrocarbon fuels. However, precisely controlling the cleavage of C−O bonds remains challenging. Here, we synthesized an oil-soluble precursor NiMo₆-DODA by encapsulating the polyoxometalates (POMs) (NH₄)₄[NiMo₆O₂₄H₆] (NiMo₆) with surfactants, followed by in-situ construction of an ultra-dispersed monolayer NiMoS catalyst. The “surfactant shell” of the precursor ensured its homogeneous dispersion in the oil phase, while gradually sacrificing and decomposing during the sulfidation to mitigate the aggregation of the MoS₂ nanosheets. Meanwhile, the well-defined “POMs core” established an atomic-level Ni-Mo proximity, ensuring the dominance of the Ni-promoted MoS₂ active phase. This design not only altered the adsorption configuration of esters on the NiMo catalyst but also introduced abundant edge sulfur vacancies to promote oxygen atom adsorption and accelerate C−O bond cleavage. The results showed that NiMo₆-DODA achieved 100% conversion of methyl palmitate and 100% alkane selectivity under low catalyst loading conditions. Notably, the selectivity for n-hexadecane reached 94.2%, significantly surpassing that obtained with a commercial oil-soluble precursor (69.8%). Furthermore, the catalyst maintained high activity across multiple reaction cycles and in the solvent-free conversion of real bio-oils. This strategy of pre-assembly combined with sacrificial sulfidation provides a simple and effective route for designing hydrodeoxygenation catalysts that enable precise control over ester C−O bond cleavage.

Key words: Hydrodeoxygenation, Oil-soluble catalyst, Polyoxometalates, NiMoS Active phases, Monolayer MoS₂

Chongzheng Xu, Haoping Di, Fengyue Sun, Wenjing Bao, Yanwei Ju, Dengwei Yan, Changle Yue, Yiyuan Xu, Yunxiu Zhao, Shuo Wang, Jiqian Wang, Yukun Lu. Achieving selective C−O bond cleavage of esters over monolayer NiMoS catalysts derived from oil-soluble polyoxometalates[J]. Chinese Journal of Catalysis, 2026, 87: 327-341.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65104-2

https://www.cjcatal.com/EN/Y2026/V87/I8/327

Figures/Tables 10

Scheme 1. Adsorption of fatty acids and esters.

Fig. 1. (a) Schematic diagram of the synthesis of NiMo6-DODA. (b) XRD patterns. (c) FT-IR spectra. (d) 1H NMR spectra. TG and DTG image of NiMo6 (e) and NiMo6-DODA (f). (g) H2-TPR profiles.

Fig. 2. XRD patterns (a) and Raman spectra (b) of sulfided catalysts.

Fig. 3. TEM images (a), slab lengths (b), and stacking numbers (c) of sulfided catalysts.

Fig. 4. XPS spectra of Mo 3d (a), Ni 2p (b), and S 2p (c). FT-IR spectra of CO adsorbed on S-NiMo6-DODA (d), S-acNi&acMo (e), and S-NiMo6 (f). (g) FT-IR spectra of pyridine adsorbed on sulfided catalysts at 200 °C. (h) H2-TPR profiles of sulfided catalysts. (i) EPR spectra.

Fig. 5. (a,b) AC-HAADF-STEM images of S-NiMo6-DODA. (c) Intensity maps along the corresponding dashed line in (b). The labels 1S and 2S denote one sulfur atom and two sulfur atoms, respectively. (d) HAADF-STEM images and corresponding EDS mapping of S-NiMo6-DODA.

Fig. 6. (a) HDO performance of methyl palmitate on different precursors. (b?d) Optimization of reaction conditions on NiMo6-DODA catalyst. (e,f) FT-IR spectra of samples obtained at different reaction times. (g) The proposed reaction pathway of methyl palmitate on the NiMo6-DODA catalyst.

Fig. 7. Products distribution of methyl palmitate hydrogenation at different temperature over 300 °C (a) and 340 °C (b). (c) Linear fit of lnki (i = 1?5) to 1/T and corresponding activation energies. Conversion and product yield fitting curves of methyl palmitate on NiMo6-DODA at 300 °C (d), 320 °C (e), and 340 °C (f). (g) Recycling of NiMo6-DODA for hydro-conversion of methyl palmitate. (h) XRD patterns of spent S-NiMo6-DODA. (i) Solvent-free hydro-conversion of other feeds with NiMo6-DODA. (j) O/C and carbon balance of oils before and after solvent-free reaction. (k) Comparison of the performance of various catalysts for the HDO reaction of bio-oils and fats.

Fig. 8. Proposed reaction pathway diagram of methyl palmitate on NiMo6-DODA.

Fig. 9. Structural guidance effect of oil-soluble precursor NiMo6-DODA on the adsorption configuration of oils on the catalyst.

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