Enhanced photocatalytic activity of S-doped graphitic carbon nitride hollow microspheres: Synergistic effect, high-concentration antibiotic elimination and antibacterial behavior

For the past few years, graphitic carbon nitride (g-C3N4) has been widely used to eliminate environmental pollutants, but limited active site on surface and low separation/migration ability suppress its practical uses. Herein, we adopted a supramolecular self-assembly route followed with S doping to synthesize S-doped g-C3N4 with a hollow microsphere composition (SCNHM), where the shell was demonstrated to compose of ultrathin nanosheets. The unique structural characteristics endow the SCNHM with high specific surface area (-81 m2 g-1) to provide abundant reaction sites and enhanced light-harvesting due to the light-scattering effect of hollow structure. Moreover, the S dopant meliorated the electronic structure to narrow the bandgap and promoted the charge separation/transfer capability. With this synergistic effect, the SCNHM presented greatly improved photocatalytic activity for degrading tetracycline hydrochloride (TC) compared to the CN, SCN and CNHM samples. This photocatalyst could eliminate high-concentration TC (50 mg L-1) in 18 min, and the 30 min removal efficiencies of 100 mg L-1 and 200 mg L-1 reached 92 % and 60 %, which is much better than the reported photocatalysts in literatures (usually <= 20 mg L-1). Additionally, the good photocatalytic durability was confirmed and the degradation pathway of TC was proposed. Furthermore, the SCNHM was proved to meanwhile possess superior performance for inactivating the typical Gram-positive bacterium of Staphylococcus aureus (S. aureus) and the typical Gram-negative bacterium of Escherichia coli (E. coli). Finally, based on determination of band alignment and detection of active species, a plausible photocatalytic mechanism was proposed.

Automated summary

In this study, S-doped graphitic carbon nitride (SCNHM) with a hollow microsphere structure and ultrathin nanosheets was synthesized through supramolecular self-assembly and S-doping. The SCNHM showed improved photocatalytic activity for degrading tetracycline hydrochloride and also exhibited excellent photocatalytic durability and bactericidal activity against Staphylococcus aureus and Escherichia coli.