Efficient removal of perfluoroalkyl acids (PFAAs), especially short-chain ones, from contaminated water is of great challenge and is urgently called for so as to safeguard the ecosystem and human health. Herein, polypyrrole (PPy) functionalized biochar (BC) composites were innovatively synthesized by an in situ self-sacrificial approach to allow efficient capture of PFAAs with different chain lengths. Compared with conventional PPy-based composites synthesized by direct polymerization using FeCl3 as an oxidizing agent, PPy/BC composites were fabricated utilizing freshly generated Fe3+ as an oxidizing agent from self-sacrificial Fe3O4 for pyrrole monomers in situ polymerizing on BC. As a result, with the support of BC and gradual release of Fe3+, PPy overcame its tendency to aggregate and became uniformly dispersed on BC, and meanwhile, PPy could well tailor the surface chemistry of BC to endow its positively charged surface. Consequently, the composites exhibited strong sorption capacities of 3.89 and 1.53 mmol/g for short-chain perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS), 2.55 and 1.22 mmol/g for long-chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), respectively, which were superior to those of pristine BC, commercial activated carbon, and anion exchange resins reported. Additionally, they could effectively remove 17 different classes of per- and polyfluoroalkyl substances (PFAS) (removal >95%) from actual PFAS-contaminated water, and the spent sorbent could be well regenerated and reused at least 5 times. An integrated analysis indicated that such an outstanding PFAA sorption performance on PPy/BC composites could be mainly attributed to surface adsorption enhanced by electrostatic attractions (anion exchange interaction) with the traditional hydrophobic interaction and pore filling of less contribution, particularly for short-chain analogues. These results are expected to inform the design of BC with greater ability to remove PFAS from water and the new sorbent could help water facilities comply with PFAS regulations.
