Key factors and microscopic mechanisms controlling adsorption of cadmium by surface oxidized and aminated biochars

Modified biochar has great potential for adsorbing cadmium (Cd) in the aquatic environment, but the micro-immobilization mechanisms, driven by surface modifications, remain unclear. There has been no attempt to determine the key adsorption factors by integrating the numerous physiochemical indicators. In this study, surface oxidized biochar (OPBC) and surface aminated biochar (APBC) were prepared from porous biochar (PBC), and the Cd adsorption mechanisms by the modified biochars at the molecular and electronic scales were investigated. The adsorption capacity of APBC and OPBC for Cd was 23.54 and 19.04 mg g^-1, respectively, which was about three times higher than that of PBC. Macroscopically, physicochemical adsorption and intraparticle diffusion dominated the Cd adsorption, and surface properties, such as functional groups, were identified as key factors controlling adsorption. Microscopically, the adsorption of Cd mainly occurred in regions rich in π electrons, lone pair electrons and electron donor groups. The interaction between carboxyl and Cd dominated the adsorption performance of OPBC, while the Cd²⁺-π interaction was weakened by increasing the π electron electrostatic potential of aromatic rings. The lone pair electrons of the amino groups dominated the complexation of APBC with Cd, and the π electron electrostatic potential was almost unaffected.