A new composite by coupling chalcopyrite (CuFeS
2) with silver phosphate (Ag
3PO
4) (CuFeS
2/Ag
3PO
4) was proposed by using a cyclic microwave heating method. The prepared composites were characterized by scanning and transmission electron microscopy and X-ray diffraction, Fourier-transform infrared, UV–Vis diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. Under optimum conditions and 2.5 W irradiation (wavelength length > 420 nm, power density = 0.38 Wcm
−2), 96% of rhodamine B (RhB) was degraded by CuFeS
2/Ag
3PO
4 within a 1 min photo-Fenton reaction, better than the performance of Ag
3PO
4 (25% degradation within 10 min), CuFeS
2 (87.7% degradation within 1 min), and mechanically mixed CuFeS
2/Ag
3PO
4 catalyst. RhB degradation mainly depended on the amount of hydroxyl radicals generated from the Fenton reaction. The degradation mechanism of CuFeS
2/Ag
3PO
4 from the photo-Fenton reaction was deduced using a free radical trapping experiment, the chemical reaction of coumarin, and photocurrent and luminescence response. The incorporation of CuFeS
2 in Ag
3PO
4 enhanced the charge separation of Ag
3PO
4 and reduced Ag
3PO
4 photocorrosion as the photogenerated electrons on Ag
3PO
4 were transferred to regenerate Cu
2+/Fe
3+ ions produced from the Fenton reaction to Cu
+/Fe
2+ ions, thus simultaneously maintaining the CuFeS
2 intact. This demonstrates the synergistic effect on material stability. However, hydroxyl radicals were produced by both the photogenerated holes of Ag
3PO
4 and the Fenton reaction of CuFeS
2 as another synergistic effect in catalysis. Notably, the degradation performance and the reusability of CuFeS
2/Ag
3PO
4 were promoted. The practical applications of this new material were demonstrated from the effective performance of CuFeS
2/Ag
3PO
4 composites in degrading various dyestuffs (90–98.9% degradation within 10 min) and dyes in environmental water samples (tap water, river water, pond water, seawater, treated wastewater) through enhanced the Fenton reaction under sunlight irradiation.
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