Direct Oxidation of Hibiscus cannabinus Stalks to Vanillin Using CeO₂ Nanostructure Catalysts

Biomass lignin can be used to produce vanillin through an oxidation process. Although its purity is high, the processing time and separation efficiency are not ideal. This research aims to produce vanillin directly from Kenaf stalks without separating the lignin first from the lignocellulosic biomass. This method is greener because it does not require the separation of cellulose and hemicellulose from the biomass, thus minimizing the use of acid and alkaline solutions and saving time. A high oxygen storage capacity and release capacity of ceria as an oxidation catalyst contribute to the reversable redox properties between Ce⁴⁺ and Ce³⁺ in ceria lattice. Cerium oxide nanostructures were synthesized using a hydrothermal method treated under alkaline NaOH, followed by drying at 120 °C for 16 h and calcining at different temperatures between 400 and 600 °C for the direct oxidation of Kenaf stalks to vanillin under microwave irradiation. The catalysts were characterized for their physicochemical properties using XRD, N₂ adsorption-desorption isotherms and TEM. All synthesized CeO₂ nanostructures showed the presence of diffraction peaks assigned to the presence of cubic fluorite. The N₂ adsorption-desorption isotherms showed that all catalysts possess a Type IV isotherm, indicating a mesoporous structure. The TEM image shows the uniform shape of the CeO₂ nanostructures, while HRTEM images show that the CeO₂ nanostructures are single-crystalline in nature. All catalysts were tested for the direct oxidation of Kenaf stalks using H₂O₂ as the oxidizing agent in temperatures ranging from 160 to 180 °C for 10-30 min with 0.1-0.3 g catalyst loading under 100-500 W of microwave irradiation. The CeO₂-Nps-400 catalyst produced the highest vanillin yields of 3.84% and 4.32% for the direct oxidation of Kenaf stalks and extraction of lignin from Kenaf stalks, respectively. Compared to our earlier study, the highest vanillin yields of 2.90% and 3.70% for direct biomass and extracted lignin were achieved using a Ce/MgO catalyst.