Cobalt-Graphene Catalyst for Selective Hydrodeoxygenation of Guaiacol to Cyclohexanol

Herein, cobalt-reduced graphene oxide (rGO) catalyst was synthesized with a practical impregnation-calcination approach for the selective hydrodeoxygenation (HDO) of guaiacol to cyclohexanol. The synthesized Co/rGO was characterized by transmission electron microscopy (TEM), high-angle annular dark-field scanning TEM (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, X-ray diffraction (XRD), and H₂ temperature-programmed reduction (H₂-TPR) analysis. According to the comprehensive characterization results, the catalyst contains single Co atoms in the graphene matrix and Co oxide nanoparticles (CoO_x) on the graphene surface. The isolated Co atoms embedded in the rGO matrix form stable metal carbides (CoC_x), which constitute catalytically active sites for hydrogenation. The rGO material with proper amounts of N heteroatoms and lattice defects becomes a suitable graphene material for fabricating the catalyst. The Co/rGO catalyst without prereduction treatment leads to the complete conversion of guaiacol with 93.2% selectivity to cyclohexanol under mild conditions. The remarkable HDO capability of the Co/rGO catalyst is attributed to the unique metal-acid synergy between the CoC_x sites and the acid sites of the CoO_x nanoparticles. The CoC_x sites provide H while the acid sites of CoO_x nanoparticles bind the C-O group of reactants to the surface, allowing easier C-O scission. The reaction pathways were characterized based on the observed reaction-product distributions. The effects of the process parameters on catalyst preparation and the HDO reaction, as well as the reusability of the catalyst, were systematically investigated.