Nitrogen-rich porous biochar is produced by direct pyrolysis, combined with K2CO3 or ZnO activation using soybean residue as raw material, their adsorption performance and mechanism for perchlorate are investigated. The results show that the activation process significantly enhances the biochar's adsorption capacity for perchlorate, the saturated adsorption capacities of BK800 and BZ600 increase by 9 and 15 times, respectively. The adsorption process adheres to the Langmuir isotherm model and pseudo-second-order kinetic model, indicating predominant monolayer and chemical adsorption. Pore filling, hydrogen bond and electrostatic interactions play key roles in the adsorption of perchlorate on biochar. The adsorption performance of K2CO3-activated biochar improves with increasing pyrolysis temperature, attributed to the expansion of the biochar's specific surface area (BK800, 1371.7 m2 g−1). Conversely, ZnO-activated biochar exhibits high adsorption performance due to its mesoporous channels and abundant N, O-functional groups (BZ600: 1.86 % N content), despite having a lower specific surface area. Density functional theory (DFT) calculations determine the adsorption energies of perchlorate on various functional groups of biochar, with pyrrole N exhibiting the highest interaction, followed by -OH, -COOH, graphite N, and pyridine N. Acidic conditions promote stronger electrostatic attraction in the functional groups of biochar. Therefore, the adsorption performance of biochar to perchlorate can be improved by targeted modification of its micropore structure, O-functional groups and pyrrole N structures.
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