• Mechanical activation significantly reduces particle size and increases surface area and energy of chalcopyrite and pyrite, enhancing their reactivity.
• The combined use of mechanically activated chalcopyrite and pyrite boosts copper extraction by 51.8% compared to non-activated mixtures, reaching 63.4%.
• Pyrite's catalytic role in chalcopyrite bioleaching is activated by mechanical activation, providing additional oxidants and acting as a cathode in galvanic coupling.
• A mechanistic model is proposed to explain how mechanical activation promotes pyrite's role in accelerating chalcopyrite bioleaching.
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