Toward improving porous carbon performance for adsorption of short-chain PFAS: Exploring the effects of S- and N-...

Highly porous carbon black was modified by the incorporation of sulfur and nitrogen groups to a carbon matrix. Thiourea or 1-amino-2-naphthol-4-sulfonic acid (ANSA) were used as carbon modifiers. A thermal treatment with thiourea introduced more N and S heteroatoms than that with ANSA and the latter decreased surface area and porosity. Pyridines, pyrroles and thiophenes/sulfides were identified on the surfaces. Carbons were tested as the adsorbents of short-chain PFAS- nonafluorobutane-1-sulfonic acid (PFBS) and heptafluorobutyric acid (PFBA). Surface chemistry played the most important role when S and N species were incorporated into the surface. The pyridines and sulfides increased the adsorption due to electrostatic interactions with negatively charged anions, and pyrroles contributed to hydrogen binding through interactions with oxygen in acid heads. The results suggested the London dispersion forces between fluorine in hydrophobic chains with reduced sulfur species, increasing PFAS adsorption. The numbers of PFAS molecules adsorbed at the relatively high equilibrium concentrations were similar regardless the length of the chain or chemistry of the acid head, suggesting the strong effect of the combination of steric effects and the quantitative availability of adsorption sites, including pores and specific adsorption centers. They determined the spatial location of the molecules on the surfaces.