A comparative study of chemical treatment by MgCl2, ZnSO4, ZnCl2, and KOH on physicochemical properties and acetaminophen adsorption performance of biobased porous materials from tree bark residues

Preparing sustainable and highly efficient biomass-based carbon materials (BBPM) as adsorbents remains a challenge for organic pollutant management. In this work, novel biobased carbon material has been synthesized via facile, sustainable, and different single-step pyrolysis chemical methods (KOH, ZnCl₂, ZnSO_4, and MgCl₂) using a Norway spruce bark as suitable and efficient carbon precursor. The effects of each chemical activator on the physicochemical structure of synthesized were thoroughly investigated as well as its performance on the acetaminophen adsorption. The results showed that the use of different chemical activation provoked remarkable differences in the BBPM physicochemical characteristics. The KOH activation generated material with the highest specific surface area (2209 m² g⁻¹), followed by ZnCl₂ (1019 m² g⁻¹), ZnSO₄ (446 m² g⁻¹), and MgCl₂ (98 m² g⁻¹). The chemical characterization of the carbon materials indicated that the activation of MgCl₂ yielded a material around three times more hydrophobic when compared with the other activation methods. The acetaminophen removal showed to be ultrafast, not only due to the BBPM's microstructure but also to the abundant active sites provided by the different chemical activation methods. The adsorption equilibrium times were reached at 1 min for BBPM-KOH and BBPM-MgCl₂ and 15 min for BBPM-ZnSO₄ and BBPM-ZnCl₂. The adsorption process suggests that the pore-filling mechanism mainly dominates the acetaminophen removal but also some physical-chemical interactions such as hydrogen bonding between the amide group of acetaminophen and oxygenated or nitrogenated groups of biochar, π-π interactions between the aromatic ring of the pharmaceutical and the aromatics of biochar, n-π interaction, van der Waals interactions. The BBPM regeneration studies showed very good cyclability; in the 3rd cycle, the removal was approximately 70% for all four samples. The samples were also used to treat two synthetic effluents, which attained a removal percentage up to 91.9%.