Sulfur-modified chitosan derived N,S-co-doped carbon as a bifunctional material for adsorption and catalytic degradation sulfamethoxazole by persulfate.

N,S-co-doped carbons were synthesized through the calcination of sulfur-modified chitosan for the first time, and utilized as persulfate activators for sulfamethoxazole (SMX) remediation in water. The chitosan and sulfonyl chloride underwent one-step sulfonylation reaction to generate S-modified chitosan. The catalyst NSC-3 showed both excellent adsorption and catalytic oxidation efficiency, corresponding 98.62% removal and 81.34% mineralization rate within 90 min. The rate constant (kobs) was up to 0.0578 min-1, with 75.60-folders higher than that of sulfur-free catalyst NC (7.6580 ×10-4 min-1). The synergy of N and S contributed to the improvement of removal efficiency. The adsorption and oxidation performance were highly depended on the S/N atomic ratio. At the S/N ratio of 0.18, the maximum adsorption and oxidation capability were obtained. The NSC-3/PS system exhibited outstanding adaptability at the wide pH range from 3.07 to 9.28, while the inhibitory effect occurred at strong basic conditions (pH = 11.01). The thiophene sulfur and structural defects were identified as the catalytic sites in activating PS. Both radical and non-radical pathways were responsible for degradation process, where 1O2 played a major role, SO4·-exerted a minor contribution, and O2·- acts as the precursor for the production of 1O2. Another source of 1O2 was assigned to the activation of PS by structure defects. This work indicates that N,S-co-doped carbon at an optimal S/N atomic ratio effectively catalyzes persulfate, and provides an innovative method to construct bifunctional carbon materials of adsorption and oxidization.