A metal-free Z-scheme PPy/MCN heterojunction for antibiotic removal via synergism of photocatalysis and peroxymonosulfate activation

Developing an active and synergistic system based on photocatalysis and peroxymonosulfate (PMS) activation is considered an effective strategy for efficient removal of antibiotics. However, photocatalytic heterojunctions generally comprise metallic catalysts that can cause metal leaching and secondary pollution, and a clear understanding of the synergy between photocatalysis and PMS activation is still missing. Herein, a metal-free Zscheme polypyrrole (PPy)/melamine-derived graphitic carbon nitride (MCN) heterojunction photocatalyst was synthesized via calcination and in-situ loading for catalyzing the degradation of ciprofloxacin (CIP) and other emerging pollutants in a visible light-emitting diode (LED)/PMS synergistic system, which showed a significantly higher activity than the single LED and PMS systems. The optimal 0.5 %PPy/MCN (0.5 % is the mass ratio of PPy in the mixture of PPy/MCN) performed well under a wide pH range (3-11), while exhibiting superior antiinterference for common water constituents and outstanding reusability and stability. The 0.5 %PPy/MCN/ LED/PMS synergistic system showed the highest kinetic constant (0.0643 1/min), which increased 3.00, 6.77 and 2.91-fold over the 0.5 %PPy/MCN/PMS, 0.5 %PPy/MCN/LED, and MCN/LED/PMS system, respectively. Mechanistic investigation and theoretical calculations revealed that PPy, with its high conductivity and strong light absorption ability, facilitated the generation and separation of e+/h+ in the 0.5 %PPy/MCN/LED/PMS system and activated PMS for generating reactive species such as 1O2, which degraded cCIP together with h+. Furthermore, electron transfer pathway (ETP) was elucidated using electrochemical characterizations. CIP was degraded via ring opening, cleavage hydroxylation, ammonia oxidation and elimination reactions, which substantially reduced the toxicity of CIP. Overall, this study may help the rational design of metal-free catalysts and provide a deep insight for the LED/PMS synergistic mechanisms.