S-doping α-Fe2O3 induced efficient electron-hole separation for enhanced persulfate activation toward carbamazepine oxidation: Experimental and DFT study

Abstract As a typical iron-based oxide semiconductor with abundant reserves, α-Fe2O3 has been widely used in the domain of photocatalysis and environmental remediation. Here, sulfur doped α-Fe2O3 (S-α-Fe2O3) has been successfully fabricated through coprecipitation, hydrothermal and calcination processes and applied to activate persulfate (PS) for carbamazepine (CBZ) degradation under UV irradiation. Systematic characterizations were conducted to analyze the morphology, structure and chemical composite of S-α-Fe2O3. UV/PS/S-α-Fe2O3 process showed remarkably enhanced photocatalytic performance for CBZ degradation. The degradation rate constant (7.78×10-2 min-1) was about 2.2 and 14.1 times as high as that of UV/PS/α-Fe2O3 (3.60×10-2 min-1) and UV/PS (5.53×10-3 min-1) processes, respectively. With increasing PS concentration and photocatalyst dosage, the removal efficiency of CBZ both increased. UV/PS/S-α-Fe2O3 process can efficiently and steadily operate in a wide pH range of 3.0-8.0. The introduction of water matrix species (i.e. chloride, bicarbonate, nitrate and humic acid) exerted different effects on CBZ degradation. S-dopant was doped via forming ≡FeIII-SO42- bond on S-α-Fe2O3 surface, and doped sulfur functioned as surface electrons trapping centers derived from DFT study. The band gap value of S-α-Fe2O3 was reduced and the separation efficiency of photogenerated electrons and holes was improved. Hydroxyl radicals, sulfate radicals, superoxide radicals and holes all contributed to CBZ destruction. Furthermore, two major routes of CBZ degradation were proposed as hydroxylation and deamination, then followed by decarbonxylation, ketonization and ring cleavage based on the results of HPLC-MS and DFT calculation.