S-doped MIL-53 as efficient heterogeneous electro-Fenton catalyst for degradation of sulfamethazine at circumneutral pH

The reduced S-modified MIL-53(Fe) was prepared by sulfurizing MIL-53(Fe) at low temperature, which was an efficient electro-Fenton catalyst at wide pH range (3-9) for sulfamethazine (SMT) degradation. The best temperature and MIL-53(Fe)/S ratio were 350 °C and 1:2, at which the BET surface area was much enlarged. The MIL-53(Fe) surface was etched by S to many 2D nanosheets with the thickness of ~50 nm, while S2-2 replaced OH- to coordinate with Fe2+ and increased the Fe2+ content, which improved the catalytic performance. Even at initial pH of 7.0, the SMT removal was 95.8%, and the rate constant (k) in the Hetero-EF process was 16-folds of that in the Homo-EF process. The turnover frequency (TOFd) value of MIL-53(Fe)/S(1:2)-350 was 0.48 L g-1 min-1, which was 6.8 times that of commercial FeS2. The S2-2in catalyst adjusted the pH superfast, and promoted the generation of Fe2+ and thus efficiently activating H2O2 to form surface ·OH, which was verified to be the main radical by EPR and radical scavenger experiments. This catalyst showed promising prospect for environmental application and could be regenerated by sulfidation method. S-doped MIL-53(Fe) was an excellent pH regulator, thus promoting promising application in Hetero-EF processes.