Photocatalytic degradation under ultra-low powered light is a viable advanced oxidation process technique against extensive emerging contaminants. As a new and remarkable class of nanoporous materials, metal-organic frameworks (MOFs), attract interest for the supreme adsorptive and photocatalytic functionalities. An outstanding MOF, MIL-101(Fe) chosen as a photocatalyst template for the synthesis of α-Fe2O3 by a simple thermal modification to improve the structural properties toward methylene blue (MB) eradication. Octahedron-like α-Fe2O3 photocatalyst (Modified MIL-101(Fe), M-MIL-101(Fe)) was superior in dispersion and separation properties in aqueous medium. Moreover, the adsorptive and catalytic performance was increased for modified form by ~ 7.3% and ~ 17.1% compared to pristine MIL-101(Fe), respectively. Synergistic improvement of MB removal achieved by simultaneous adsorption/degradation under 5-W LED irradiation. Parametric study indicated an 18.1% and 44.5% improvement in MB removal was observed by increasing pH from 4 to 10, and M-MIL-101(Fe) dose from 0.2 to 1 g L−1, respectively. MB removal followed the pseudo-second-order kinetics model and the process efficiency dropped by 38% as MB concentration increased from 5 to 20 mg L−1. Radical trapping tests revealed the significant role of $${\mathrm{OH}}^{.}$$
OH
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and electron radicals as the major participants in dye degradation. A significant loss in the efficiency of M-MIL-101(Fe) was observed in the reusability tests that is good to study further. In conclusion, a simple thermal post-synthesis modification on MIL-101(Fe) improved its structural, catalytic, and adsorptive properties against MB.