Kinetic and Thermodynamic Studies of Methylene Blue Adsorption on Biomass-Derived Biocarbon Materials

In this study, biocarbon adsorbents were obtained from fennel and caraway seeds through microwave-assisted chemical activation with sodium carbonate. The activation process involved carbonizing the raw material at 300 °C for 30 min., followed by impregnation with sodium carbonate at a precursor-to-activator mass ratio of 1:2. Activation was performed at two distinct temperatures-500 °C and 600 °C-with an activation time of 15 min. The structural, textural, and surface chemical characteristics of the obtained biocarbons were investigated using complementary analytical techniques, including low-temperature nitrogen adsorption-desorption isotherms, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Boehm titration, and pH analysis of aqueous extracts. The resulting adsorbents demonstrated low development of specific surface area (109-154 m²/g) and limited sorption capacity for methylene blue (20-32 mg/g). Adsorption experiments indicated that the Freundlich isotherm model most accurately described the data, suggesting multilayer adsorption on heterogeneous surfaces. Thermodynamic evaluations showed the adsorption to be both spontaneous and endothermic. The adsorption mechanism is primarily governed by electrostatic interactions between the cationic dye and surface functional groups, π-π interactions with the carbon structure, and diffusion within mesopores. This study provides a comparative evaluation of microwave-assisted Na₂CO₃ activation of fennel and caraway seed waste and assesses the potential of these biochars for dye removal from aqueous solutions.