Unraveling the outstanding catalytic efficiency of unprocessed bone-derived biochar: A deep dive into the mechanisms of native organic encapsulation and defective nitrogen doping in boosting persulfate activation for tetracycline degradation

Designing efficient non-metallic catalysts for persulfate (PS) activation has attracted broad attention due to their demonstrated immense potential in environmental remediation. In this study, unprocessed pig bone waste was successfully converted into biochars (PBCs) through a straightforward one-step pyrolysis process, which function as efficient PS catalysts for the removal of tetracycline (TC). The results revealed that the endogenous inner layer hydroxyapatite activator (IHA) and the rich native outer layer organic component wrapped with nitrogen-doped additives (OONA) found in raw bone-derived waste biomass collaborate to exert a dual effect of template and surface modification at 900 ℃. Notably, under this synergistic action, 900PBC exhibited active defect nitrogen (pyridinic and graphitic nitrogen), sp2-hybridized groups (C = C, C = O, and C = N) and high defect levels (ID/IG = 1.0291), along with a cross-linked micro-mesoporous structure. This unique combination of properties endowed 900PBC with excellent catalytic activity, enabling it to effectively remove 50 mg/L of TC in the PS system within 30 min, primarily through a dual reaction pathway involving oxygen-active species (O2·-, 1O2) and electron transfer (fitting instantaneous-current values to PS concentrations, R2 = 0.95). Density-functional theory calculations confirmed that, within the nitrogen configurations located at defect sites, pyridinic nitrogen exerted a significant influence on the electron cloud density of adjacent carbon networks, subsequently promoting the formation of excited states of PS. Meanwhile, graphitic nitrogen constructed electron bridges with adjacent sp2-hybridized orbitals, facilitating the formation of the metastable complex 900PBC-PS*. Remarkably, 900PBC also exhibited excellent cyclic stability, maintaining a 93 % TC removal rate after four cycles, as well as high tolerance to a broad pH range (3–9), high concentrations of coexisting ions (10 mM), and diverse real-world water bodies. This study offers novel insights into synthesizing high-value biochar from waste bones with high catalytic activity.