Carbon-coated Ni-Co alloy catalysts: preparation and performance for in-situ aqueous phase hydrodeoxygenation of methyl palmitate to hydrocarbons using methanol as the hydrogen donor

Abstract

Carbon-coated Ni, Co and Ni-Co alloy catalysts were prepared by the carbonization of the metal doped resorcinol-formaldehyde resins synthesized by the one-pot extended Stöber method. It was found that the introduction of Co remarkably reduced the carbon microsphere size. The metallic Ni, Co, and Ni-Co alloy particles (mainly 10–12 nm) were uniformly distributed in carbon microspheres. A charge transfer from Ni to Co appeared in the Ni-Co alloy. Compared with those of metallic Ni and Co, the d-band center of the Ni-Co alloy shifted away from and toward the Fermi level, respectively. In the in-situ aqueous phase hydrodeoxygenation of methyl palmitate with methanol as the hydrogen donor at 330 °C, the decarbonylation/decarboxylation pathway dominated on all catalysts. The Ni-Co@C catalysts gave higher activity than the Ni@C and Co@C catalysts, and the yields of n-pentadecane and n-C₆–n-C₁₆ reached 71.6% and 92.6%, respectively. The excellent performance of Ni-Co@C is attributed to the electronic interactions between Ni and Co and the small carbon microspheres. Due to the confinement effect of carbon, the metal particles showed high resistance to sintering under harsh hydrothermal conditions. Catalyst deactivation is due to the carbonaceous deposition, and the regeneration with CO₂ recovered the catalyst reactivity.

Key words： Stöber method; carbon-coated Ni-Co alloy; in-situ hydrodeoxygenation; methyl palmitate; decarbonylation/decarboxylation

Acknowledgements

The authors gratefully acknowledge support from the National Natural Science Foundation of China (Grant Nos. 21576193 and 21176177).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-021-2079-1 and is accessible for authorized users.

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