Revealing the pH-Dependent Adsorption Dynamics of Tetracycline Hydrochloride on Phosphoric Acid-Activated Corncob Biochar

Aquaculture wastewater containing tetracycline hydrochloride (TCH) poses significant environmental problems and health risks. We investigated the adsorption of TCH onto phosphoric acid-activated corncob biochar (PCC) as a sustainable and efficient removal strategy. PCC was synthesized from cob feedstock activated by phosphoric acid under a pyrolysis temperature of 300 °C in a limited-air atmosphere. It was characterized extensively, revealing a high specific surface area (1071.75 m2/g), high porosity with total pore volume of 0.912 cm3/g, and abundant surface functional groups including phosphate, carboxylic, and amine groups. Batch adsorption experiments demonstrated an ultrahigh adsorption capacity for TCH, with a maximum theoretical capacity (Langmuir model) of 953.62 mg/g at 313 K. Its adsorption isotherms transfer from Langmuir type to Freundlich type as temperature rises, indicating a transition from monolayer to multilayer adsorption. The adsorption kinetics were governed by a synergistic mechanism involving surface adsorption and a pore-filling effect (intra-particle diffusion). Critically, the adsorption dynamics exhibit an intra-particle diffusion-controlled process at a low pH (3.0) during the final stage of adsorption. Strong hydrogen bonding led to high initial adsorption rates, and the adsorption converted to diffusion-controlled mode eventually. In contrast, at higher pH (≥7.0), electrostatic repulsion between PCC adsorbents and TCH molecules hindered intra-particle diffusion, causing the final adsorption stage to deviate from diffusion control. This work provides comprehensive insights into the pH-dependent interfacial interactions and kinetics governing TCH removal by corncob-derived, phosphoric acid-activated biochar.