A binary Fe
2O
3/Fe
3O
4 mixed nanocomposite was prepared by phyto-mediated avenue to be suited in the photo-Fenton photodegradation of methylene blue (MB) in the presence of H
2O
2. XRD and SEM analyses illustrated that Fe
2O
3 nanoparticles of average crystallite size 8.43 nm were successfully mixed with plate-like aggregates of Fe
3O
4 with a 15.1 nm average crystallite size. Moreover, SEM images showed a porous morphology for the binary Fe
2O
3/Fe
3O
4 mixed nanocomposite that is favorable for a photocatalyst. EDX and elemental mapping showed intense iron and oxygen peaks, confirming composite purity and symmetrical distribution. FTIR analysis displayed the distinct Fe-O assignments. Moreover, the isotherm of the developed nanocomposite showed slit-shaped pores in loose particulates within plate-like aggregates and a mesoporous pore-size distribution. Thermal gravimetric analysis (TGA) indicated the high thermal stability of the prepared Fe
2O
3/Fe
3O
4 binary nanocomposite. The optical properties illustrated a narrowing in the band gab (Eg = 2.92 eV) that enabled considerable absorption in the visible region of solar light. Suiting the developed binary Fe
2O
3/Fe
3O
4 nanocomposite in the photo-Fenton reaction along with H
2O
2 supplied higher productivity of active oxidizing species and accordingly a higher degradation efficacy of MB. The solar-driven photodegradation reactions were conducted and the estimated rate constants were 0.002, 0.0047, and 0.0143 min
−1 when using the Fe
2O
3/Fe
3O
4 nanocomposite, pure H
2O
2, and the Fe
2O
3/Fe
3O
4/H
2O
2 hybrid catalyst, respectively. Therefore, suiting the developed binary Fe
2O
3/Fe
3O
4 nanocomposite and H
2O
2 in photo-Fenton reaction supplied higher productivity of active oxidizing species and accordingly a higher degradation efficacy of MB. After being subjected to four photo-Fenton degradation cycles, the Fe
2O
3/Fe
3O
4 nanocomposite catalyst still functioned admirably. Further evaluation of Fe
2O
3/Fe
3O
4 nanocomposite in photocatalytic remediation of contaminated water using a mixture of MB and pyronine Y (PY) dyestuffs revealed substantial dye photodegradation efficiencies.
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