Core–shell structured cobalt oxide nanoparticles and single Co atoms supported on graphene for selective hydrodeoxygenation of syringol to cyclohexanol†

Abstract

Heretofore selective hydrodeoxygenation (HDO) of syringol remained limited and challenging due to the complicated structure of syringol compared to other lignin-derived model compounds such as guaiacol and phenol. Here, we report an efficient HDO of syringol to cyclohexanol (CYHAOL) over a reduced graphene oxide (rGO)-supported Co catalyst (Co/rGO) capable of heterolytic dissociation of H₂ molecules. A combination of characterization methods, including HAADF-STEM, XPS, XRD, etc., and experiments reveals that Co/rGO has a unique morphology composed of core–shell structured multivalent Co oxide nanoparticles (CoO_x) incorporating oxygen vacancies distributed on the graphene surface, and high-density single Co atoms embedded in the graphene matrix, both of which can afford the highly active H^{δ −} species for the HDO reaction. The morphologies of the supported Co species are highly dependent on the graphene textures. The Co/rGO catalyst without pre-reduction treatment demonstrated exceptional catalytic activity in the HDO of syringol with high selectivity to CYHAOL under mild conditions and good stability in the catalyst components. The metal-oxide-based Co/rGO catalyst does not require the pre-reduction treatment, simplifying the catalyst preparation process and eliminating the severe sintering of the metal species.