The presence of iron atoms on the marmatite surface hinders effective interaction between the activator and the mineral, leading to unsatisfactory flotation performance through direct copper (Cu) activation. Hence, this study introduced ammonium sulfate to enhance the marmatite-activation capability by Cu ions. Additionally, the reinforcement mechanism was investigated through microflotation tests, atomic force microscopy (AFM), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and density-functional theory (DFT) calculations. Microflotation results demonstrated that the addition of ammonium sulfate as a complexing reagent increased the flotation recovery of marmatite by 17.36%. AFM analysis revealed that marmatite subjected to enhanced activation (i.e., in the presence of ammonium sulfate) exhibited a considerably higher surface roughness than that subjected to direct Cu activation. Moreover, the average height of hill-shaped materials on the marmatite surface notably increased to 9.6 nm after enhanced Cu activation. SEM-EDS analysis revealed that the concentration of Cu atoms (2.2%) on the marmatite surface after enhanced Cu activation was nearly three times that (0.8%) after direct Cu activation. Additionally, XPS results indicated a considerably higher presence of the Cu–S component on the marmatite surface after enhanced Cu activation than after direct Cu activation. ToF-SIMS analysis indicated an increase in the fragment peaks of Cu+, CuOCS2+, OCS2−, and OC2H2S2− on the surface of enhanced-activated marmatite. Additionally, DFT calculations indicated that the presence of NH3 molecules enhanced electron transfer between Cu and S on the hydrated marmatite surface. The marmatite (1 1 0) surface exhibited more negative adsorption energy of Cu ions after the action of NH3 molecules, and NH3–Cu showed a more stable adsorption configuration than Cu. Therefore, the addition of ammonium sulfate enhanced the Cu activation for marmatite, thereby improving flotation performance.
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