Phosphoric acid pretreatment enhances the specific surface areas of biochars by generation of micropores

Biochars are being increasingly applied in soil for carbon sequestration, fertility improvement, as well as contamination remediation. Phosphoric acid (H₃PO₄) pretreatment is a method for biochar modification, but the mechanism is not yet fully understood. In this work, biochars and the raw biomass were treated by H₃PO₄ prior to pyrolysis. Due to an acid catalysis and crosslink, the micropores of the pretreated particles were much more than those without H₃PO₄ pretreatment, resulting in the dramatical enhancement of specific surface areas of the pretreated particles. Crystalline cellulose (CL) exhibited a greater advantage in the formation of micropores than of amorphous lignin (LG) with H₃PO₄ modification. The formation mechanisms of micropores were: (a) H⁺ from H₃PO₄ contributes to micropores generation via H⁺ catalysis process; (b) the organic phosphate bridge protected the carbon skeleton from micropore collapse via the crosslinking of phosphate radical. The sorption capacities to carbamazepine (CBZ) and bisphenol A (BPA) increased after H₃PO₄ modification, which is ascribed to the large hydrophobic surface areas and more abundant micropores. Overall, H₃PO₄ pretreatment produced biochars with large surface area and high abundance of porous structures. Furthermore, the H₃PO₄ modified biochars can be applied as high adsorbing material as well as P-rich fertilizer.