The severe water pollution from effluent dyes threatens human health. This study created pH-magnetic-photocatalytic polymer microspheres to conveniently separate the photocatalyst nanoparticles from the treated water by applying an external magnetic field. While fabricating magnetic nanoparticles’ (MNPs) microspheres, incorporating 0.5 wt.% iron oxide (Fe3O4) showed the best magnetophoretic separation ability, as all the MNPs microspheres were attracted toward the external magnet. Subsequently, hybrid organic–inorganic polyoxometalates (HPOM), a self-synthesized photocatalyst, were linked with the functionalized magnetic nanoparticles (f-MNPs) to prepare augmented magnetic-photocatalytic microspheres. The photodegradation dye removal efficiency of the augmented magnetic-photocatalytic microspheres (f-MNPs-HPOM) was then compared with that of the commercial titanium dioxide (TiO2) photocatalyst (f-MNPs-TiO2). Results showed that f-MNPs-HPOM microspheres with 74 ± 0.7% photocatalytic removal efficiency better degraded methylene orange (MO) than f-MNPs-TiO2 (70 ± 0.8%) at an unadjusted pH under UV-light irradiation for 90 min. The excellent performance was mainly attributed to the lower band-gap energy of HPOM (2.65 eV), which required lower energy to be photoactivated under UV light. The f-MNPs-HPOM microspheres demonstrated excellent reusability and stability in the photo-decolorization of MO, as the microspheres retained nearly the same removal percentage throughout the three continuous cycles. The degradation rate was also found to follow the pseudo-first-order kinetics. Furthermore, f-MNPs-HPOM microspheres were pH-responsive in the photodegradation of MO and methylene blue (MB) at pH 3 (acidic) and pH 9 (alkaline). Overall, it was demonstrated that using HPOM photocatalysts in the preparation of magnetic-photocatalytic microspheres resulted in better dye degradation than TiO2 photocatalysts.
